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  1. Abstract

    The factors that control strain partitioning along plate boundaries and within continental interiors remains poorly resolved. Plate convergence may be accommodated via distributed crustal shortening or discrete crustal‐scale strike‐slip faulting, but what controls these differing modes of deformation is debated. Here we address this question by examining the actively deforming regions that surround the Tarim Basin in central Asia, where deformation is uniquely partitioned into predominately strike‐slip faults in the east and distributed fold‐thrust belts in the west to accommodate Cenozoic India‐Asia plate convergence. We present integrated geological and geophysical observations to elucidate patterns in crustal deformation and compositional structure in and around the Tarim Basin. The thrust‐dominated western Tarim Basin correlates with a strongly‐magnetic lower crust, whereas strike‐slip faulting along the eastern margins of the Tarim Basin lack such magnetic signals. We suggest that the lower crust of the western Tarim is more mafic and stronger than in the east, which impacts intra‐plate strain partitioning. A stronger lower crust results in vertical decoupling to drive mid‐crust horizontal detachments and facilitate thrust faulting, whereas a more homogenized crust favored vertical transcrustal strike‐slip faulting. These rheological differences likely originated from the impingement of the Permian Tarim plume focused in the west. A comparison with the Longmen Shan of eastern Tibetan Plateau reveals remarkably similar strain partitioning that correlates with variations in foreland rheology. Our results highlight how variations in lower‐crust viscosity impact strain partitioning in an intra‐plate setting and how plume processes exert a strong control on later continental tectonic processes.

     
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    Free, publicly-accessible full text available November 1, 2024
  2. Deformation-resistant cratons comprise >60% of the continental landmass on Earth. Because they were formed mostly in the Archean to Mesoproterozoic, it remains unclear if cratonization was a process unique to early Earth. We address this question by presenting an integrated geological-geophysical data set from the Tarim region of central Asia. This data set shows that the Tarim region was a deformable domain from the Proterozoic to early Paleozoic, but deformation ceased after the emplacement of a Permian plume despite the fact that deformation continued to the north and south due to the closure of the Paleo-Asian and Tethyan Oceans. We interpret this spatiotemporal correlation to indicate plume-driven welding of the earlier deformable continents and the formation of Tarim’s stable cratonic lithosphere. Our work highlights the Phanerozoic plume-driven cratonization process and implies that mantle plumes may have significantly contributed to the development of cratons on early Earth. 
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  3. Abstract

    Polymers with low ceiling temperatures (Tc) are highly desirable as they can depolymerize under mild conditions, but they typically suffer from demanding synthetic conditions and poor stability. We envision that this challenge can be addressed by developing high-Tcpolymers that can be converted into low-Tcpolymers on demand. Here, we demonstrate the mechanochemical generation of a low-Tcpolymer, poly(2,5-dihydrofuran) (PDHF), from an unsaturated polyether that contains cyclobutane-fused THF in each repeat unit. Upon mechanically induced cycloreversion of cyclobutane, each repeat unit generates three repeat units of PDHF. The resulting PDHF completely depolymerizes into 2,5-dihydrofuran in the presence of a ruthenium catalyst. The mechanochemical generation of the otherwise difficult-to-synthesize PDHF highlights the power of polymer mechanochemistry in accessing elusive structures. The concept of mechanochemically regulating theTcof polymers can be applied to develop next-generation sustainable plastics.

     
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  4. Fluorinated polymers are important functional materials for a broad range of applications, but the recycling of current fluorinated polymers is challenging. We present the first example of semi-fluorinated polymers that can undergo chemical recycling to form the corresponding monomers under ambient conditions. Prepared through ring-opening metathesis polymerization of functionalized trans -cyclobutane fused cyclooctene ( t CBCO) monomers, these polymers show tunable glass transition temperatures (−2 °C to 88 °C), excellent thermal stability (decomposition onset temperatures >280 °C) and hydrophobicity (water contact angles >90°). The hydrophobicity of the semi-fluorinated polymers was further utilized in an amphiphilic diblock copolymer, which forms self-assembled micelles with a size of ∼88 nm in an aqueous solution. Finally, through an efficient, regioselective para -fluoro-thiol substitution reaction, post-polymerization functionalization of a polymer with a pentafluorophenyl imide substituent was achieved. The ease of preparation, functionalization, and recycling, along with the diverse thermomechanical properties and demonstrated hydrophobicity make the t CBCO-based depolymerizable semi-fluorinated polymers promising candidates for sustainable functional materials that can offer a solution to a circular economy. 
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  5. Conjugated molecules have been typically utilized as either hole or electron extraction layers to boost the device performance of perovskite solar cells (PSCs), formed from three-dimensional (3D) perovskites, due to their high charge carrier mobility and electrical conductivity. However, the passivating role of conjugated molecules in creating two-dimensional (2D) perovskites has rarely been reported. In this study, we report novel conjugated aniline 3-phenyl-2-propen-1-amine (PPA) based 2D perovskites and further demonstrate efficient and stable PSCs containing a (PPA) x (MAPbI 3 ) 1− x /MAPbI 3 bilayer thin film (where MA is CH 3 NH 3 + ). The (PPA) x (MAPbI 3 ) 1− x /MAPbI 3 bilayer thin film possesses superior crystallinity and passivated trap states, resulting in enhanced charge transport and suppressed charge carrier recombination compared to those of a 3D MAPbI 3 thin film. As a result, PSCs containing the (PPA) x (MAPbI 3 ) 1− x /MAPbI 3 bilayer thin film exhibit a power conversion efficiency (PCE) of 21.98%, which is approximately a 25% enhancement compared to that of the MAPbI 3 thin film. Moreover, un-encapsulated PSCs containing the (PPA) x (MAPbI 3 ) 1− x /MAPbI 3 bilayer thin film retain 50% of their initial PCE after 1200 hours in an ambient atmosphere (25 °C, and 30 ± 10 humidity), whereas PSCs with the 3D MAPbI 3 thin film show significant degradation after 100 hours and a degradation of more than 50% of their original PCE after 500 hours. These results demonstrate that the incorporation of conjugated molecules as organic spacer cations to create 2D perovskites on top of 3D perovskites is an effective way to approach high-performance PSCs. 
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  6. Abstract

    Chemical recycling to monomer (CRM) is a promising route for transitioning to a circular polymer economy. To develop new CRM systems with useful properties, it is important to understand the effects of monomer structure on polymerization/depolymerization behavior. In earlier work, this group demonstrated chemically recyclable polymers prepared by ring‐opening metathesis polymerization oftrans‐cyclobutane fused cyclooctenes (tCBCO). Here, it is investigated how different substituents on cyclobutane impact the thermodynamics and thermal properties oftCBCO polymers. Introducing additional substituents to acis‐diester functionalizedtCBCO is found to favor the conversion of polymerization; increased polymerization conversion is also observed when thecis‐diester is isomerized into itstranscounterpart. The effects of these structural features on the thermal properties are also studied. These findings can provide important insights into designing next‐generation CRM polymers.

     
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