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At least 55 records · Page 3

Assessment of Composite Delamination Self-Healing Under Cyclic Loading

Recently, the promise of self-healing materials for enhanced autonomous durability has been introduced using a micro-encapsulation technique where a polymer based healing agent is encapsulated in thin walled spheres and embedded into a base polymer along with a catalyst phase. For this study, composite skin-stiffener flange debonding specimens were manufactured from composite prepreg containing interleaf layers with a polymer based healing agent encapsulated in thin-walled spheres. Constant amplitude fatigue tests in three-point bending showed the effect of self-healing on the fatigue response of the skin-stiffener flange coupons. After the cycling that created debonding, fatigue tests were held at the mean load for 24 hours. For roughly half the specimens tested, when the cyclic loading was resumed a decrease in compliance (increase in stiffness) was observed, indicating that some healing had occurred. However, with continued cycling, the specimen compliance eventually increased to the original level before the hold, indicating that the damage had returned to its original state. As was noted in a prevoius study conducted with specimens tested under monotonically increasing loads to failure, healing achieved via the micro-encapsulation technique may be limited to the volume of healing agent available relative to the crack volume.

O'Brien, T. Kevin↗

Polymer-Grafted Nanoparticles as All-in-One Nanoplatforms

Polymer-grafted nanoparticles (PGNPs) represent a versatile class of hybrid nanomaterials, in which nanoparticle cores and tethered polymer coronas are integrated into structurally programmable building blocks. Rapid advances in nanoparticle surface functionalization and surface-initiated polymerization have enabled increasingly precise control over the nanoparticle core composition and brush architecture, greatly expanding the accessible structural and functional landscape of PGNPs. This review summarizes recent progress in the modular design and structural regulation of PGNPs, with an emphasis on nanoparticle platforms and associated surface functionalization strategies, polymer brush synthesis and architectural control, and the structure−property relationships that govern PGNP behavior. Emerging applications are further highlighted, including additive manufacturing, self-healing materials, membrane-based gas separations, and battery-related systems, where PGNPs provide unique opportunities to couple nanoscale interfacial design with macroscopic performance. Finally, future opportunities are discussed for extending PGNP concepts to increasingly complex, multifunctional, and application-oriented hybrid materials.

functional nanocomposites↗

pH Sensitive Microcapsules for Delivery of Corrosion Inhibitors

A considerable number of corrosion problems can be solved by coatings. However, even the best protective coatings can fail by allowing the slow diffusion of oxygen and moisture to the metal surface. Corrosion accelerates when a coating delaminates. Often, the problems start when microscopic nicks or pits on the surface develop during manufacturing or through wear and tear. This problem can be solved by the incorporation of a self-healing function into the coating. Several new concepts are currently under development to incorporate this function into a coating. Conductive polymers, nanoparticles, and microcapsules are used to release corrosion-inhibiting ions at a defect site. The objective of this investigation is to develop a smart coating for the early detection and inhibition of corrosion. The dual function of this new smart coating system is performed by pH-triggered release microcapsules. The microcapsules can be used to deliver healing agents to terminate the corrosion process at its early stage or as corrosion indicators by releasing dyes at the localized corrosion sites. The dyes can be color dyes or fluorescent dyes, with or without pH sensitivity. Microcapsules were formed through the interfacial polymerization process. The average size of the microcapsules can be adjusted from 1 to 100 micron by adjusting the emulsion formula and the microcapsule forming conditions. A typical microcapsule size is around 10 microns with a narrow size distribution. The pH sensitivity of the microcapsule can also be controlled by adjusting the emulsion formula and the polymerization reaction time. Both corrosion indicator (pH indicator) and corrosion inhibitor containing microcapsules were formed and incorporated into paint systems. Test panels of selected steels and aluminum alloys were painted using these paints. Testing of compatibility between the microcapsule system and different paint systems are in progress. Initial experiments with the microcapsule containing paint show visible color changes at induced corrosion sites and improvement of corrosion protection. Further investigation of the performance of the coating using electrochemical techniques and long term exposure are currently underway.

Li, Wenyan↗

NASA Tech Briefs, May 2013

Topics include: Test Waveform Applications for JPL STRS Operating Environment; Pneumatic Proboscis Heat-Flow Probe; Method to Measure Total Noise Temperature of a Wireless Receiver During Operation; Cursor Control Device Test Battery; Functional Near-Infrared Spectroscopy Signals Measure Neuronal Activity in the Cortex; ESD Test Apparatus for Soldering Irons; FPGA-Based X-Ray Detection and Measurement for an X-Ray Polarimeter; Sequential Probability Ratio Test for Spacecraft Collision Avoidance Maneuver Decisions; Silicon/Carbon Nanotube Photocathode for Splitting Water; Advanced Materials and Fabrication Techniques for the Orion Attitude Control Motor; Flight Hardware Packaging Design for Stringent EMC Radiated Emission Requirements; RF Reference Switch for Spaceflight Radiometer Calibration; An Offload NIC for NASA, NLR, and Grid Computing; Multi-Scale CNT-Based Reinforcing Polymer Matrix Composites for Lightweight Structures; Ceramic Adhesive and Methods for On-Orbit Repair of Re-Entry Vehicles; Self-Healing Nanocomposites for Reusable Composite Cryotanks; Pt-Ni and Pt-Co Catalyst Synthesis Route for Fuel Cell Applications; Aerogel-Based Multilayer Insulation with Micrometeoroid Protection; Manufacturing of Nanocomposite Carbon Fibers and Composite Cylinders; Optimized Radiator Geometries for Hot Lunar Thermal Environments; A Mission Concept: Re-Entry Hopper-Aero-Space-Craft System on-Mars (REARM-Mars); New Class of Flow Batteries for Terrestrial and Aerospace Energy Storage Applications; Reliability of CCGA 1152 and CCGA 1272 Interconnect Packages for Extreme Thermal Environments; Using a Blender to Assess the Microbial Density of Encapsulated Organisms; Mixed Integer Programming and Heuristic Scheduling for Space Communication; Video Altimeter and Obstruction Detector for an Aircraft; Control Software for Piezo Stepping Actuators; Galactic Cosmic Ray Event-Based Risk Model (GERM) Code; Sasquatch Footprint Tool; and Multi-User Space Link Extension (SLE) System.

Source record↗

Covalent adaptable networks for electrolyte–binder integration in recyclable lithium metal batteries

Lithium-metal batteries (LMBs) are considered a promising next-generation energy storage technology due to their exceptionally high energy density. However, the development of solid polymer electrolytes and cathode binders for LMBs faces critical challenges, including interfacial instability, poor recyclability, and growing environmental concerns. In particular, current systems often rely on non-recyclable components featuring permanently crosslinked networks and polyfluoroalkyl substances (PFAS), such as poly(vinylidene fluoride) (PVDF), which cause battery waste and environmental harm. Herein, we introduce a multifunctional covalent adaptable network (CAN) platform based on thermally reversible Diels–Alder (DA) chemistry, designed for dual functionality as a CAN-based electrolyte (CAE) and a CAN-based cathode binder. The CAE achieves high ionic conductivity and strong storage modulus (1.4 mS cm −1 and ∼ 10 5 Pa at room temperature, respectively) and enables stable long-term cycling in symmetric Li||Li cells for over 2000 h with low overpotential. When it is applied as a cathode binder in LiFePO 4 (LFP) composite electrodes (C-LFP), the CAN matrix significantly reduces interfacial resistance and enhances discharge capacity compared to conventional PVDF-based systems. Thermal treatment induces self-healing at the cathode–electrolyte interface, further improving contact and yielding a discharge capacity of 150 mAh g −1 at 0.5 C. Moreover, the dynamic CAN architecture allows efficient recovery and reuse of lithium salts from spent electrolytes through retro-DA reactions under mild conditions (∼80 °C), establishing a low-energy, cost-effective recycling pathway. In conclusion, this work presents a scalable and sustainable strategy for high-performance LMBs by integrating recyclability, interfacial healing, and PFAS-free design, offering a holistic solution aligned with circular economy principles and next-generation battery demands.

Diels–Alder↗

Self-Healable Electrical Insulation for High Voltage Applications

Polymeric aircraft electrical insulation normally degrades by partial discharge with increasing voltage, which causes excessive localized Joule heating in the material and ultimately leads to dielectric failure of the insulator through thermal breakdown. Developing self-healing insulation could be a viable option to mitigate permanent mechanical degradation, thus increasing the longevity of the insulation. Instead of relying on catalyst and monomer-filled microcapsules to crack, flow, and cure at the damaged sites described in well-published mechanisms, establishment of ionic crosslinks could allow for multiple healing events to occur with the added benefit of achieving full recovery strength under certain thermal environments. This could be possible if the operating temperature of the insulator is the same as or close to the temperature where ionic crosslinks are formed. Surlyn, a commercial material with ionic crosslinks, was investigated as a candidate self-healing insulator based off prior demonstrations of self-healing behavior. Thin films of varying thicknesses were investigated and the effects of thickness on the dielectric strength were evaluated and compared to representative polymer insulators. The effects of thermal conditioning on the recovery strength and healing were observed as a function of time following dielectric breakdown. Moisture absorption was also studied to determine if moisture absorption rates in Surlyn were lower than that of common polyimides.

electrical insulation↗

Nature-Inspired Motivation for Developing Self-Healable Electrical Insulation

Polymeric aircraft electrical insulation normally degrade by partial discharge with increasing voltage, which causes excessive localized Joule heating in the material and ultimately leads to dielectric failure of the insulator through thermal breakdown. Self-healing insulation may be a viable option to mitigate permanent mechanical degradation, thus increasing the longevity of the material. Instead of relying on catalyst and monomer-filled microcapsules to crack, flow, and cure at the damaged sites described in well-published mechanisms, self-healing through establishment of ionic crosslinks allows for multiple healing events to occur as well as achieving full recovery strength under certain thermal environments. Surlyn®, a commercial ionically-crosslinked material, was investigated as a self-healing insulation candidate based on prior demonstrations of self-healing behavior. Thin films of varying thicknesses were investigated and the effects of thickness on the dielectric strength were evaluated and compared to representative polymer insulators. The effects of thermal conditioning on the recovery strength and healing were observed as a function of time following dielectric breakdown. Moisture absorption was studied to determine if moisture absorption rates in Surlyn® were lower than that of common polyimide insulators. Preliminary data showed that when cut, Surlyn® films lost nearly 60 percent of its original dielectric strength. However, when Surlyn® was cut and subsequently annealed, the films not only re-mended, but also recouped approximately 93 percent of its original dielectric strength, along with 90-97 percent of its mechanical strength.

electrical↗

Pyroelectric conversion in space: A conceptual design study

Pyroelectric conversion is potentially a very lightweight means of providing electrical power generation in space. Two conceptualized systems approaches for the direct conversion of heat (from sunlight) into electrical energy using the pyroelectric effect of a new class of polar polymers were evaluated. Both of the approaches involved large area thin sheets of plastic which are thermally cycled by radiative input and output of thermal energy. The systems studied are expected to eventually achieve efficiencies of the order of 8% and may deliver as much as one half kilowatt per kilogram. In addition to potentially very high specific power, the pyroelectric conversion approaches outlined appear to offer low cost per watt in the form of an easily deployed, flexible, strong, electrically ""self-healing'', and high voltage sheet. This study assessed several potential problems such as plasma interactions and radiation degradation and suggests approaches to overcome them. The fundamental technological issues for space pyroelectric conversion are: (1) demonstration of the conversion cycle with the proposed class of polymers, (2) achievement of improved dielectric strength of the material, (3) demonstration of acceptable plasma power losses for low altitude, and (4) establishment of reasonable lifetime for the pyroelectric material in the space environment. Recommendations include an experimental demonstration of the pyroelectric conversion cycle followed by studies to improve the dielectric strength of the polymer and basic studies to discover additional pyroelectric materials.

Olsen, R. B.↗

Simulation of Impact on a Ductile Polymer Plate

Explicit finite element calculations were used to visualize the deformation and temperature rise in an elastic-plastic plate impacted by a rigid projectile. Results were compared to results of experiments involving ballistic penetration of a "self-healing" thermoplastic. The calculated temperature rise agreed well with the experimental observation, but the total energy absorbed in the penetration event was underestimated in the calculation, which neglected friction.

Cremona, Rebecca L.↗

Mechanoresponsive Healing Polymers

Methods are provided to produce new mechanoresponsive healing systems. Additionally, various embodiments provide a two tier self-healing material system concept that provides a non-intrusive method to mitigate impact damage in a structure ranging from low velocity impact damage (e.g., crack damage) to high velocity impact damage (e.g., ballistic damage.) The various embodiments provide the mechanophore linked polymer PBG-BCB-PBG. The various embodiments provide methods for synthesizing PBG-BCB-PBG.

Gordon, Keith L.↗

Dynamic disulfide bond networks enable self-healable and mechanically resilient intrinsically stretchable organic solar cells

A dynamic disulfide network introduced into donor/acceptor blends enables room-temperature self-healing and mechanical resilience in intrinsically stretchable organic solar cells, achieving performance recovery after high mechanical strain. The development of intrinsically stretchable organic solar cells (IS-OSCs) faces significant challenges in balancing mechanical durability and optoelectronic performance. Conventional π-conjugated polymer-based donor/acceptor blend films often exhibit limited stretchability and irreversible performance degradation under mechanical strain. To address these limitations, we propose a novel self-healable donor/acceptor blended film with a dual-network morphology, achieved by incorporating a dynamic disulfide bond-based crosslinked network into the bulk-heterojunction film. The resulting thin films demonstrate a power conversion efficiency (PCE) of 16.39% in rigid OSC devices and a fracture strain of 15.6%. Remarkably, the IS-OSCs retain 80% of their initial PCE under 30% strain and exhibit performance recovery after multiple stretch-release cycles at 40% strain through a room-temperature self-healing process. This work provides a proof-of-concept for highly stretchable and durable IS-OSCs, offering valuable insights for advancing the field of wearable energy systems, adaptive solar textiles, and sustainable electronics.

Yang, Wenyu↗

Upcycling of Polystyrene Waste to Poly(ionic liquid) Materials

The C–H functionalization of commodity polymers could be a promising approach for upcycling plastic waste into advanced materials, which can alter the properties of the original materials through the introduction of different functionalities onto the existing backbone structures. In this study, waste polystyrene (PS) was modified by Friedel–Crafts acylation using 4-chlorobutyryl chloride (4-CBC) followed by reaction with N-alkylimidazoles to form cationic polyelectrolytes. These methods provide access to what are essentially poly(ionic liquid) (poly(IL)) materials with properties that are distinctly different from those of the PS from which they were formed. In one notable example, the glass transition temperature (T g ) of imidazolium-functionalized PS was ∼16 °C, which is a nearly 90 °C reduction from PS. This is also evidenced by macroscopic mechanical properties where the poly(IL) product is highly elastic in stark contrast to brittle PS. Moreover, the resulting ionomers showed self-healing behaviors in the presence of a “free” IL further contributing to the utility of the materials. Here, the methods in this work can open opportunities to utilize waste PS to obtain a vast array of poly(IL) materials with highly tailored structures and properties.

36 MATERIALS SCIENCE↗

Incorporation of Thioacetate Pendants on a Polyalkenamer Enables High Extensibility

This study focuses on functionalizing polycyclooctene (PCOE) with thioacetate groups using thiol–ene click chemistry. The ethylene thioacetate (EVSA) copolymers produced vary in thioacetate incorporation (4–25 mol %) via a controlled semibatch addition technique with AIBN dosing. Copolymers with 4–14 mol % thioacetate are semicrystalline, while those with 20–25 mol % are amorphous. Increased functionalization correlates with decreased crystallinity and increased stretchability, with the highest functionalization (25 mol %) showing a modulus of 0.045 MPa and 2000% elongation at break. Here, this behavior is due to the pseudoprecise functionalization of the thioacetate pendants and intrinsic cross-linking that occurs during melt processing. Broadband dielectric spectroscopy (BDS) indicates a low activation energy barrier (16 kJ/mol for the β process), suggesting potential self-healing applications.

36 MATERIALS SCIENCE↗

Puncture-Healing Properties of Carbon Nanotube-Filled Ionomers

Ionomers are polymers that contain ionic groups in relatively low concentrations along the polymer backbone. These ionic groups, in the presence of oppositely charged ions, form aggregates that lead to novel physical properties of the polymer. React-A-Seal(trademark) and Surlyn(trademark) are poly(ethylene-co-methacrylic acid) (EMAA) ionomer-based materials and Nucrel(trademark) is the EMAA acid copolymer neutralized to produce Surlyn(trademark). React-A-Seal(trademark), Surlyn(trademark), and Nucrel(trademark) recover into their original shapes following a high impact puncture at velocities ranging from 300 to 1200 ft/s ('self-healing'). This self-healing process may be of great benefit in space applications where structures are exposed to matter impacts. A thermal IR camera indicated a temperature increase to 98 C for Nucrel(trademark) 925, Surlyn(trademark) 8940, React-A-Seal(trademark), and Surlyn(trademark) 8920 after initial penetration. To understand and generalize the observed phenomena, questions concerning the mechanism of the puncture resealing must be answered. One suggestion is that the elastic character of the melt created by the puncture drives the self-healing. This inference is based on the observed temperature rise of approx. 3 C above the melting temperature of the samples (approx. 95 C) during the impact. With the expectation of gaining additional insight into the self-healing phenomenon, a thermodynamic and viscoelastic investigation was conducted using primarily DSC and DMA. Surlyn(trademark) and React-A-Seal(trademark) showed the characteristic order-disorder transition at approx. 52 C that has been reported in literature. Master curves were constructed from the creep isotherms for the four EMAA samples. An aging study was performed to investigate the irreproducibility and "tailing effect" observed in the creep data. The aging study indicated that, with increased aging time and temperature, changes in the polyethylene matrix lead to complexities in morphology resulting in changes in the magnitude and shape of the creep curves.

Ward, Thomas C.↗

Self-Healing Cements with Improved Toughness at Casing and Formation Interfaces for Subsurface Applications (CRADA 530)

Over the three-year CRADA, Pacific Northwest National Laboratory (PNNL) advanced a new class of Molecular Velcro™ self-healing wellbore cements designed to improve the long-term integrity of wells used for geothermal energy production and carbon storage. Conventional wellbore cement can crack due to repeated mechanical loading, temperature swings, and exposure to aggressive subsurface fluids. Once cracks form, they can create leakage pathways, drive expensive remediation (“workovers”), and in extreme cases shorten well life. This project addressed that problem by developing polymer-modified cement systems that can autonomously re-seal cracks and better tolerate the extreme conditions experienced in subsurface wells, while remaining compatible with practical cementing operations.

15 GEOTHERMAL ENERGY↗

Self-Healing Behavior of Ethylene-Based Ionomers

The self-healing behavior of poly(ethylene-co-methacrylic acid) (EMAA)-based ionomers holds tremendous potential for use in a wide variety of unique applications. However, to effectively utilize this self-healing behavior and to design novel materials which possess this ability, the mechanism by which they heal must first be understood ionomers are a class of polymers that can be described as copolymers containing less than 15 mol% ionic content whereby the bulk properties are governed by ionic interactions within the polymer. These ionic groups aggregate into discrete regions known as multiplets which overlap forming clusters that act as physical cross-links profoundly influencing the bulk physical properties. These clusters possess an order-disorder transition (T(sub i)) where the clustered regions may rearrange themselves given time and stimuli. Recognizing the strong influence of these ionic regions on other well understood ionomer properties, their role in self-heating behavior will be assessed. The self-healing behavior is observed following projectile puncture. It has been suggested that during impact energy is passed to the ionomer material, heating it to the melt state. After penetration, it is proposed that the ionic regions maintain their attractions and flow together patching the hole. Thus, the importance of this ionic character and is unique interaction must be established. This will be accomplished through examination of materials with varying ionic content and through the analysis of the T(sub i). The specific ionomer systems examined include a number of ethylene-based materials. Materials of varying ionic content, including the non-ionic base copolymers, will be examined by peel tests, projectile impact and DSC analysis. The information will also be compared with some basic data on LDPE material.

Kalista, Stephen J., Jr.↗

NASA Tech Briefs, January 2012

Contents of this issue are: (1) Energy-Based Tetrahedron Sensor for High-Temperature, High-Pressure Environments (2) Handheld Universal Diagnostic Sensor (3) Large-Area Vacuum Ultraviolet Sensors (4) Fiber Bragg Grating Sensor System for Monitoring Smart Composite Aerospace Structures (5) Health-Enabled Smart Sensor Fusion Technology (6) Extended-Range Passive RFID and Sensor Tags (7) Hybrid Collaborative Learning for Classification and Clustering in Sensor Networks (8) Self-Healing, Inflatable, Rigidizable Shelter (9) Improvements in Cold-Plate Fabrication (10) Technique for Radiometer and Antenna Array Calibration - TRAAC (11) Real-Time Cognitive Computing Architecture for Data Fusion in a Dynamic Environment (12) Programmable Digital Controller (13) Use of CCSDS Packets Over SpaceWire to Control Hardware (14) Key Decision Record Creation and Approval Module (15) Enhanced Graphics for Extended Scale Range (16) Debris Examination Using Ballistic and Radar Integrated Software (17) Data Distribution System (DDS) and Solar Dynamic Observatory Ground Station (SDOGS) (18) Integration Manager (19) Eclipse-Free-Time Assessment Tool for IRIS (20) Automated and Manual Rocket Crater Measurement Software (21) MATLAB Stability and Control Toolbox Trim and Static Stability Module (22) Patched Conic Trajectory Code (23) Ring Image Analyzer (24) SureTrak Probability of Impact Display (25) Implementation of a Non-Metallic Barrier in an Electric Motor (26) Multi-Mission Radioisotope Thermoelectric Generator Heat Exchangers for the Mars Science Laboratory Rover (27) Uniform Dust Distributor for Testing Radiative Emittance of Dust-Coated Surfaces (28) MicroProbe Small Unmanned Aerial System (29) Highly Stable and Active Catalyst for Sabatier Reactions (30) Better Proton-Conducting Polymers for Fuel-Cell Membranes (31) CCD Camera Lens Interface for Real-Time Theodolite Alignment (32) Peregrine 100-km Sounding Rocket Project (33) SOFIA Closed- and Open-Door Aerodynamic Analyses (34) Sonic Thermometer for High-Altitude Balloons (35) Near-Infrared Photon-Counting Camera for High-Sensitivity Observations (36) Integrated Optics Achromatic Nuller for Stellar Interferometry (37) High-Speed Digital Interferometry (38) Ultra-Miniature Lidar Scanner for Launch Range Data Collection (39) Shape and Color Features for Object Recognition Search (40) Explanation Capabilities for Behavior-Based Robot Control (41) A DNA-Inspired Encryption Methodology for Secure, Mobile Ad Hoc Networks (42) Quality Control Method for a Micro-Nano-Channel Microfabricated Device (43) Corner-Cube Retroreflector Instrument for Advanced Lunar Laser Ranging (44) Electrospray Collection of Lunar Dust (45) Fabrication of a Kilopixel Array of Superconducting Microcalorimeters with Microstripline Wiring Spacecraft Attitude Tracking and Maneuver Using Combined Magnetic Actuators (46) Coherent Detector for Near-Angle Scattering and Polarization Characterization of Telescope Mirror Coatings

Source record↗

N -Terminal Octylated Peptoid Hydrogels as 3D-Printable Cell Scaffolds and Proteolytically Robust Cargo Depots

Supramolecular hydrogels that mimic the extracellular matrix (ECM) represent promising materials for tissue engineering and drug delivery. However, conventional hydrogels formed via the self-assembly of natural or synthetic building blocks often face a trade-off between biological functionality and biochemical stability, limiting their utility in long-term or protease-rich environments. Peptoids, a class of peptide-inspired, sequence-defined polymers, offer a compelling alternative due to their exceptional proteolytic resistance and bioactivity. Despite this potential, the development of supramolecular peptoid hydrogels has been hindered by the absence of backbone hydrogen bond donors, which limits long-range ordering necessary for efficient hydrogel formation. This work describes a short peptoid functionalized at the N-terminus with an octyl chain that readily self-assembles into hydrogels. Hydrophobic interactions among pendant octyl groups promote directional peptoid packing into highly ordered nanosheets, which interconnect to form a porous hydrogel network. These hydrogels exhibit tunable viscoelasticity, shear-thinning, and self-healing properties, enabling their use as inks for extrusion-based 3D printing. They support NIH-3T3 fibroblast adhesion, spreading, and proliferation, maintaining greater than 95% cell viability over 4 days. Moreover, the hydrogels retain their macroscopic integrity under protease-rich conditions, enabling sustained cargo release and uniform cellular uptake. Together, this study demonstrates a class of supramolecular peptoid hydrogelators that integrate biocompatibility, 3D printability, and proteolytic stability, providing a versatile platform for ECMmimetic scaffolds in regenerative medicine and long-term therapeutic delivery.

cargo delivery↗