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Microphase separation in homopolymer-block copolymer mixtures as function of composition, molecular weight and interaction parameters
Space weathering is an important process that affects the surfaces of airless bodies, such as (101955) Bennu. The consequences of this process include physical and chemical changes to materials on the surface, which in turn change spectral characteristics, especially in the visible to near infrared wavelengths. These spectral changes are not the same across airless bodies because the changes are dependent on the composition and mineralogy of the surface and even location within the Solar System. The main space weathering products responsible for these spectral changes are submicroscopic particles, which consist of two types, nanophase and microphase particles, and affect visible to near-infrared reflectance spectra differently. Nanophase particles are particles <33 nm in size and occur in agglutinates and within glassy patinas around regolith particles. In contrast, microphase particles are >33 nm in size and are present only within agglutinates. These spectral differences are best illustrated by lunar samples. In lunar soils, the nanophase and microphase particles consist of metallic iron. With increasing abundance of nanophase iron particles in a regolith, its spectrum exhibits a lower overall reflectance in the visible to near infrared, weakened absorption bands, and a reddened continuum slope. In contrast, an increasing abundance of microphase iron only causes decreases in reflectance and not reddening. Because of the spectral differences introduced by these two types of particles, it is possible to model the nanophase and microphase particle abundances of a surface through the radiative transfer technique. Beyond the Moon, the composition of the nanophase and microphase particles can include other phases because the mineralogy of the surfaces of other planetary bodies is different. For example, the nanophase and microphase particles may consist of amorphous carbon (Mercury) and sulfides (Itokawa). The mineralogy of Bennu is consistent with carbonaceous chondrites. From a number of space weathering experiments on CM chondrites, the likely nanophase and microphase mineral phases on Bennu includes iron, magnetite, and sulfides (i.e., pentlandite and troilite). The goal of this work is to input the predicted nanophase and microphase compositions for Bennu into the radiative transfer technique. Next, we use this technique to model the OSIRIS-REx Visible Infrared Spectrometer (OVIRS) so that we can model the nanophase and microphase particle abundances across the surface. This will result in space weathering maps of the surface of Bennu, which are useful for understanding the degree of space weathering across the surface and its relationship to various regions and geological features.
The surfaces of airless bodies, such as 101955 Bennu, are vulnerable to micrometeoroids, high-energy particles, and solar wind particles. As a result, material on the surface of these bodies experience physical and chemical changes that are collectively known as space weathering. Space weathering processes result in the production of sub-micronsized particles called submicroscopic particles. There are two types of submicroscopic particles, nanophase (<33 nm in size) and microphase particles (>33 nm in size). Studies of lunar samples show that nanophase particles occur within the glassy rims that surround grains and agglutinates. In contrast, microphase iron particles occur only within agglutinates. Another important difference between these two particles is that nanophase and microphase particles affect visible to near-infrared reflectance spectra differently. From lunar samples, the presence of nanophase particles in a regolith causes the regolith’s reflectance spectrum to darken and redden, whereas the presence of microphase particles in a regolith causes it to only darken. In addition, the reflectance spectra of submicroscopic particle-bearing regolith exhibit weakened absorptions and spectral features. Lantz et al. (2018) found that these particles also affect spectral curvature [8]. By taking advantage of these spectral characteristics, with global spectral data, it is possible to model the nanophase and microphase particle abundances across a planetary surface resulting in the production of global space weathering maps.
The surfaces of airless bodies such as lunar and S-type asteroids typically become spectrally redder in visible to near-infrared reflectance with longer exposures to space weathering. However, some carbonaceous asteroids instead become spectrally bluer. Space weathering experiments on carbonaceous meteorites have provided some clues as to the space weathering products that could produce spectral bluing. We applied these experimental results to our Hapke radiative transfer model, with which we modeled spectral data from the OSIRIS-REx mission in order to determine whether these space weathering products—specifically, nanophase and microphase metallic iron, troilite, and magnetite—could explain the globally blue spectrum of the carbonaceous asteroid (101955) Bennu. The model suggests that the surface of Bennu has microphase iron, nanophase magnetite, and nanophase and microphase troilite. Considering previous space weathering experiments together with our spectral modeling of Bennu, we posit that the presence of nanophase magnetite is what causes a carbonaceous asteroid to become spectrally bluer with exposure time. Nanophase magnetite can form on asteroids that have Fe-bearing hydrated minerals (phyllosilicates). On anhydrous carbonaceous asteroids, nanophase iron forms instead of magnetite, leading to spectral reddening. We therefore predict that samples returned by the OSIRIS-REx mission from Bennu will have more nanophase magnetite than nanophase iron with nanophase and microphase sulfides, whereas samples returned by the Hayabusa2 mission from the carbonaceous asteroid (162173) Ryugu, which is spectrally red, will contain nanophase and microphase sulfides as well as more nanophase iron than nanophase magnetite.
The ultimate goal of the research in smart structures and smart materials is the development of a new generation of products/devices which will perform better than products/devices built from passive materials. There are a few examples of multilayer polymer systems which function as smart structures, e.g. a synthetic muscle which is a multilayer assembly of a poly(ethylene) layer, a gold layer, and a poly(pyrrole) layer immersed in a liquid electrolyte. Oxidation and reductions of the active pyrrole layer causes the assembly to reversibly deflect and mimic biological muscles. The drawback of such a setup is slow response times and the use of a liquid electrolyte. We have developed multifunctional polymers which will eliminate the use of a liquid electrolyte, and also because the functionalities of the polymers are within a few hundred angstroms, an improved response time to changes in the external field should be possible. Such multifunctional polymers may be classified as the futuristic 'smart materials.' These materials are composed of a number of different functionalities which work in a synergistic fashion to function as a device. The device performs on the application of an external field and such multifunctional polymers may be scientifically labeled as 'field responsive polymers.' Our group has undertaken a systematic approach to develop functional and multifunctional polymers capable of functioning as field responsive polymers. Our approach utilizes multicomponent polymer systems (block copolymers and graft copolymers), the strategy involves the preparation of block or graft copolymers where the functionalities are limited to different phases in a microphase separated system. Depending on the weight (or volume) fractions of each of the components, different microstructures are possible. And, because of the intimate contact between the functional components, an increase in the synergism between the functionalities may be observed. In this presentation, three examples of multifunctional polymers developed in our labs will be reported. The first class of multifunctional polymers are the microphase separated mixed (ionic and electronic) conducting or MIEC block copolymers. The second class being developed in our labs are the biocompatible conductive materials and the conductive fluids. The final class may be considered microwave active smart polymers.
Block copolymers are a class of relatively new materials which contain long sequences of two (or more) chemically different repeat units. Unlike random copolymers, each segment may retain some properties which are characteristic of its homopolymer. It is well known that most physical blends of two different homopolymers are incompatible on a macro-scale. By contrast most block copolymers display only a microphase (eg. 100-200 A domains) separation. Complete separation is restricted because of a loss in configurational entropy. The latter is due to presence of chemical bond(s) between the segments. Novel physical properties can be obtained because it is possible to prepare any desired combination of rubber-like, glassy, or crystalline blocks. The architecture and sequential arrangement of the segments can strongly influence mechanical behavior.
The microstructure of silicon carbide whiskers grown from rice hulls has been studied using methods of high-resolution analytical electron microscopy. Small, partially crystalline inclusions (about 10 nm) containing calcium, manganese, and oxygen are concentrated in whisker core regions, while peripheral regions are generally inclusion free. The distinct microphase distribution is evidence of a two-stage growth process in which the core region grows first, followed by normal growth toward whisker sides. Partial dislocations extend radially from the core region to the surface and tend to be paired in V-shaped configurations. Whisker surfaces exhibit microroughness due to a tendency to develop small facets on close-packed planes. The microstructural data obtained from TEM observations are used as a basis for discussion of the mechanisms involved in whisker growth, and a model of the growth process is proposed. The model includes a two-dimensional growth mechanism involving vapor, liquid, and solid phases, although it is significantly different from the classical vapor-liquid-solid (VLS) process of whisker growth.
Rod-coil molecules have been introduced as a novel type of block copolymers with unique microstructure due to their ability to self-assemble to various ordered morphologies on a nanometer length scale. These molecules, comprised two homo polymers joined together at one end, microphase separate into ordered, periodic arrays of spheres, cylinders in the bulk state and or solution. To get ordered structure in a reasonable scale, additional force field are applied, such as mechanical shearing, electric field and magnetic field. Recently, progress has made it a possible to develop a new class of polyimides (PI)-Polyethylene oxide (PEO) that are soluble in polar organic solvents. The solvent-soluble PI-PEO has a wide variety of applications in microelectronics, since these PI-PEO films exhibit a high degree of thermal and chemical stability. In this paper, we report the self-assembled ordered structure of PI-PEO molecules formed from concentrate solution.
While the ability of proteins to self-assemble makes them powerful tools in nanotechnology, in biological systems protein-based structures ultimately depend on the context in which they form. We combine the self-assembling properties of synthetic diblock copolymers and proteins to construct intricately ordered, three-dimensional polymer protein structures with the ultimate goal of forming nano-scale devices. This hybrid approach takes advantage of the capabilities of organic polymer chemistry to build ordered structures and the capabilities of genetic engineering to create proteins that are selective for inorganic or organic substrates. Here, microphase-separated block copolymers coupled with genetically engineered heat shock proteins are used to produce nano-scale patterning that maximizes the potential for both increased structural complexity and integrity.