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At least 199 records · Page 11

Symmetry-Breaking and Self-Sorting in Block Copolymer-Based Multicomponent Nanocomposites

Co-assembly of inorganic nanoparticles (NPs) and nanostructured polymer matrix represents an intricate interplay of enthalpic or entropic forces. Particle size largely affects the phase behavior of the nanocomposite. Theoretical studies indicate that new morphologies would emerge when the particles become comparable to the soft matrix's size, but this has rarely been supported experimentally. By designing a multicomponent blend composed of NPs, block copolymer-based supramolecules, and small molecules, a 3-D ordered lattice beyond the native BCP's morphology was recently reported when the particle is larger than the microdomain of BCP. The blend can accommodate various formulation variables. In this work, when the particle size equals the microdomain size, a symmetry-broken phase appears in a narrow range of particle sizes and compositions, which we named the "train track" structure. In this phase, the NPs aligned into a 3-D hexagonal lattice and packed asymmetrically along the c axis, making the projection of the ac and the bc plane resemble train tracks. Computational studies show that the broken symmetry reduces the polymer chain deformation and stabilizes the metastable hexagonally perforated lamellar morphology. Given the mobility of the multicomponent blend, the system shows a self-sorting behavior: segregating into two macroscopic phases with different nanostructures based on only a few nanometers NP size differences. Smaller NPs form "train track" morphology, while larger NPs form a "simple hexagon" structure, where the NPs take a symmetric hexagonal arrangement. Detailed structural evolution and simulation studies confirm the systematic-wide cooperativity across different components, indicating the strong self-regulation of the multicomponent system.

"train track" morphology↗

Designing a Block Copolymer Membrane for Selective Transport of Lactic Acid from Aqueous Mixtures

We report the design and synthesis of a triblock copolymer-based membrane for enabling selective transport of lactic acid from aqueous solutions. This is relevant to the production of polylactic acid, one of the few biodegradable and biobased polymers with sufficient mechanical strength for practical applications. The end blocks are positively charged with negatively charged lactate counterions. The middle block is polybutadiene (PBD). Due to microphase separation, the charged blocks form channels for transporting lactic acid. The mechanical integrity of the membrane is controlled by cross-linking the PBD block. Transport of lactic acid and water across the membrane was studied by placing the membrane between two chambers, a feed chamber containing aqueous lactic acid solutions, and a receiving chamber containing pure water. The lactic acid concentration in the receiving chamber was monitored as a function of time using conductivity, HPLC, and NMR. The corresponding flux of water from the receiving chamber to the feed chamber was measured using an NMR-based approach. The lactic acid and water permeabilities through our membrane were (1.12 ± 0.05) × 10–8 and (8.58 ± 0.75) × 10–9 cm2 s–1. To our knowledge, there are no reports of lactic acid permeabilities through any membrane in the literature. The separation factor of our membrane, αLA/water, 1.305 ± 0.123, is comparable to that of membranes used for selective transport of ethanol, despite the fact that lactic acid is a much larger molecule than ethanol. Selective transport of lactic acid in our membrane is governed mainly by differences in solubility; lactic acid is 18 times more soluble in the membrane than water.

Jana, Rounak↗

Proposed uses of laser light scattering instruments for polymerization studies

Microgravity offers a unique environment for studying polymer diffusion and polymer polymerization reactions. The absence of convection currents, which are the major mode of mixing at the molecular level on Earth, are eliminated or reduced in the microgravity environment. More importantly, the prediction of unique copolymer composition development in microgravity allows controlled formation of new compositions of matter. The absence of mixing at the molecular level should produce unique short block copolymers available for the first time for comonomer compositions which normally lead to random or long block copolymer under good mixing. The investigation of fundamental polymer diffusion and polymer polymerization processes in microgravity is proposed. This effort will involve fundamental studies of monomer and polymer diffusion; their effects on initiation, propagation, and especially termination kinetics rate constant; and the accurate evaluation of copolymerization reactivity ratios in microgravity. The experimental design is presented for these studies along with an evaluation technique for in situ monitoring of polymer diffusion and polymerization kinetics.

Mathias, Lon J.↗

Effects of Asymmetric Molecular Architecture on Chain Stretching and Dynamics in Miktoarm Star Copolymers

We use broad-band dielectric spectroscopy (BDS) and small-angle X-ray scattering (SAXS) to investigate the impact of architectural asymmetry in the miktoarm star copolymer on the dielectric polymer relaxations. The miktoarm copolymers studied contain one or two polystyrene (PS) chains of constant molecular weight and two identical poly(cis-1,4-isoprene) (PI) chains with varied molecular weights. Using the chains in the PI block as dielectric probes, we find that the architecturally asymmetric miktoarm star copolymer systems (PSPI 2 ) feature distributions in chain relaxation times and dielectric relaxation strengths that are not dependent on molecular weight or morphology, in stark contrast to the effects of morphological confinement observed for symmetric diblock systems (PS-b-PI or PS 2 PI 2 ). Along with evidence from the SAXS measurements regarding phase separation, these results are attributed to influences from chain stretching within the framework of the Gaussian chain model for block copolymer systems. As such, the molecular architecture in block copolymers happens to be a versatile handle to control polymer chain dynamics and, ultimately, the macroscopic physicochemical properties in architecturally complex polymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

PSCF+: An Extended and Improved Open-Source Software Package for Polymer Self-Consistent Field Calculations

This work introduces PSCF+, a freely available open‑source software tool for modeling how block copolymers self‑assemble into ordered nanoscale structures. The software allows researchers to study a wide range of polymer models and interaction types, making it possible to directly compare theoretical predictions with molecular and simulation‑based studies in a consistent way. PSCF+ incorporates several recently developed numerical methods that significantly reduce computer memory requirements and speed up calculations, enabling efficient use of modern GPU hardware. Here, it also provides automated tools to calculate free‑energy landscapes and phase boundaries, which are essential for understanding and predicting material behavior. Together, these advances make PSCF+ a powerful and flexible platform for studying polymer self‑assembly and support the design of new polymeric materials for scientific and technological applications.

Chemical calculations↗

Challenge Solutions for a Significant Water Cut Reduction History Match on Heavy Oil Polymer EOR

Milne Point Field is conducting the first-ever active polymer flood pilot program designed to enhance oil recovery (EOR) of heavy oils on the Alaska North Slope (ANS). The experimental field program consists of two pairs of horizontal injection and production wells deployed in an isolated fault block in the Schrader Bluff reservoir. The EOR method combines polymer flooding and low salinity water flooding to improve recovery. Prior average water cut reduction in polymer EOR fields ordinarily ranges between 10% to 15% for most light oil and heavy oil reservoirs. When comparing other field applications, the long-lasting (24 months) and much lower water cut poses a challenge for numerical history matching when applying typical simulation methods. This abstract discusses two practical new approaches used for history matching of the long-lasting ultralow water cut. These new applications include 1) multiple relative permeability curves with J-function incorporation with low endpoints of relative permeability of water (Krw). This approach integrated the permeability differential adjustment in the geometries of horizontal and vertical directions based on geological review. 2) A specific permeability channel strips along with the horizontal or vertical planar assumption. The current history matching results indicate success in achieving an excellent agreement with the field observed low water-cut.

Namie, S.↗

Facile synthesis of epoxide-co-propylene sulphide polymers with compositional and architectural control

Here, we present a facile method to produce propylene sulphide (PS) homopolymers up to 100 kg mol -1 and PS-epoxide statistical, block, and ABA copolymers using inexpensive and versatile thio-aluminium (SAl) based initiators. Homopolymerizations of PS with SAl initiators are living and controlled, with number averaged molecular weights ($\bar M$ n ) up to 100 kg mol -1 while maintaining narrow polydispersity (Ð < 1.4). Statistical and block copolymers of PS and epichlorohydrin (ECH) or propylene oxide (PO) are synthesized and characterized by size-exclusion chromatography (SEC), differential scanning calorimetry (DSC), 1 H and 13 C NMR spectroscopy, diffusion ordered spectroscopy (DOSY), and small-angle X-ray scattering (SAXS). This work represents the first statistical copolymerization of PS and epoxides with similar reactivity ratios, allowing fine control over composition. Block-copolymers of PS and epoxides are synthesized by sequential addition, without intermediate preparative steps. Polymer architecture is controlled through modification of the initiator; we synthesized a di-functional (d-H) SAl initiator to produce ABA tri-block-copolymers. Finally, poly(ethylene glycol) (PEG) was used as a macroinitiator to create PEG-b-PPS block copolymers and characterized by 1 H, 13 C NMR spectroscopy, DOSY, DSC, and SEC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Understanding Interfacial Block Copolymer Structure and Dynamics

Here, block copolymer (BCP) structure and dynamics were studied using small-angle neutron scattering (SANS), neutron spin echo (NSE) spectroscopy, and molecular dynamics (MD) simulations to obtain a fundamental understanding of the impact of an interfacial block on chain dynamics. A glassy block acted as the interface, and the dynamics of a rubbery block was studied. The rubbery block was protonated near the interface in one sample and near the chain end in another sample to observe the interfacial effect on the rubbery polymer. Analysis of the structure and dynamics revealed that the interfacial rubbery block was confined in layered morphologies and exhibited much slower dynamics than the chain-end rubbery block that was dispersed in the rubbery matrix. The interfacial rubbery block showed weaker dynamical relaxation than that at the chain end, and it also had critically important length scale dependence. Dynamical slowing was only observed at length scales significantly larger than the characteristic segmental length, and the disparity between interfacial and chain-end dynamics increased with increasing length.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Controlling Rheology of Fluid Interfaces through Microblock Length of Sequence-Controlled Amphiphilic Copolymers

Previous studies have demonstrated that films of sequence-controlled amphiphilic copolymers display contact angles that depend on microblock size. This suggests that microblock length may provide a means of tuning surface and interfacial properties. In this work, the interfacial rheology of a series of sequence-controlled copolymers, prepared through the addition of bicyclo[4.2.0]oct-1(8)-ene-8-carboxamide (monomer A) and cyclohexene (monomer B) to generate sequences up to 24 monomeric units composed of (A m B n ) i microblocks, where m, n, and i range from 1 to 6. Interfacial rheometry is used to measure the mechanical properties of an air–water interface with these copolymers. As the microblock size increases, the interfacial storage modulus, G', increases, which may be due to an increase in the size of interfacial hydrophobic domains. Small-angle X-ray scattering shows that the copolymers have a similar conformation in solution, suggesting that any variations in the mechanics of the interface are due to assembly at the interface, and not on solution association or bulk rheological properties. This is the first study demonstrating that microblock size can be used to control interfacial rheology of amphiphilic copolymers. Here, the results provide a new strategy for controlling the dynamics of fluid interfaces through precision sequence-controlled polymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Toward Thermally Stimuli-Responsive Polymeric Vesicles Fabricated by Block Copolymer Blends for Nanocarriers

Polymeric vesicles, characterized by enhanced colloidal stability, excellent mechanical properties, controllable surface functionality, and adjustable membrane thickness, are extremely useful in nano- and bio-technology for potential applications as nanosized carriers for drugs and enzymes. However, a few preparative steps are necessary to achieve a unilamellar vesicle with a narrow size distribution. Herein, we report the spontaneous formation of unilamellar polymeric vesicles with nanometer sizes (<50 nm), fabricated by simply mixing diblock copolymers (P(EO-AGE)(2K-2K) and P(EO-AGE)(0.75K-2K)) with differing hydrophilic mass fractions in aqueous solutions. Depending on the mixing ratio of block copolymers and the temperature, the block copolymer mixtures self-assemble into various nanostructures, such as spherical and cylindrical micelles, or vesicles. The self-assembled structures of the block copolymer mixtures were characterized by small-angle neutron scattering, resulting in a phase diagram drawn as a function of temperature and the mixing condition. Notably, the critical temperature for the micelle-to-vesicle phase transition can be easily controlled by altering the mixing conditions; it decreases with an increase in the concentration of one of the block copolymers.

block copolymers↗

Self-Cleaning Highly Porous TiO 2 Coating Designed by Swelling-Assisted Sequential Infiltration Synthesis (SIS) of a Block Copolymer Template

Photocatalytic self-cleaning coatings with a high surface area are important for a wide range of applications, including optical coatings, solar panels, mirrors, etc. Here, we designed a highly porous TiO 2 coating with photoinduced self-cleaning characteristics and very high hydrophilicity. This was achieved using the swelling-assisted sequential infiltration synthesis (SIS) of a block copolymer (BCP) template, which was followed by polymer removal via oxidative thermal annealing. The quartz crystal microbalance (QCM) was employed to optimize the infiltration process by estimating the mass of material infiltrated into the polymer template as a function of the number of SIS cycles. This adopted swelling-assisted SIS approach resulted in a smooth uniform TiO 2 film with an interconnected network of pores. The synthesized film exhibited good crystallinity in the anatase phase. The resulting nanoporous TiO 2 coatings were tested for their functional characteristics. Exposure to UV irradiation for 1 h induced an improvement in the hydrophilicity of coatings with wetting angle reducing to unmeasurable values upon contact with water droplets. Furthermore, their self-cleaning characteristics were tested by measuring the photocatalytic degradation of methylene blue (MB). The synthesized porous TiO 2 nanostructures displayed promising photocatalytic activity, demonstrating the degradation of approximately 92% of MB after 180 min under ultraviolet (UV) light irradiation. Thus, the level of performance was comparable to the photoactivity of commercial anatase TiO 2 nanoparticles of the same quantity. Our results highlight a new robust approach for designing hydrophilic self-cleaning coatings with controlled porosity and composition.

36 MATERIALS SCIENCE↗

Self-assembly method for core/shell nanoparticles with enhanced emission

A core/shell nanoparticle with enhanced emission comprises a fluorescent conjugated polymer core that is encapsulated by an amphiphilic block copolymer shell. The core/shell nanoparticle structure confines the electronic charge to improve quantum yield and is water soluble to enable low-cost and environmentally friendly processing.

Fan, Hongyou↗

Developing nanometer scale, atomically precise metallo-catalysts with Molecular Lego

We propose to create atomically precise, highly robust, nanometer scale macromolecules that organize biomimetic metal binding groups in designed three-dimensional pockets to accelerate specific polymerization reactions. These atomically precise catalysts will create atomically precise polymers with improved mechanical and environmental properties from renewable building blocks. We seek to create and study nanometer scale catalysts that mimic metallo-enzymes in their activity and selectivity because these larger catalysts will be able to make more extensive non-covalent contacts with the transition state of the growing polymer. These catalysts will have extended lifetimes because they will better protect the metals and higher activity because additional reactive groups can be brought in close contact with the active site to enhance reactivity. They will be far more tolerant to extremes of temperature and will not denature in non-aqueous solvents because they are held together by multiple, strong, covalent bonds. Our approach to catalysts could be used to develop catalysts to replace noble metal-based catalysts when targeting other reactions, because the geometry of the active site enforced by the Molecular Lego scaffolding will access new reactivity, mimicking how nature uses earth abundant metals for much of its catalysis. We will initially target Lewis acid-based catalysts that assemble aliphatic polyesters with improved stereoselectivity, tacticity and complex alternation of monomers. Aliphatic polyesters have received growing attention as attractive, environmentally benign, and sustainable alternatives to polymers developed from petroleum feedstocks. Aliphatic polyesters are environmentally friendly because they undergo facile hydrolytic degradation to benign products, and they have excellent properties and high biocompatibility. We will assemble these catalysts using unique “Spiroligomers” (aka Molecular Lego) chemistry developed in the Schafmeister group combined with the organometallic chemistry expertise of the Dobereiner group. Polymers are an attractive synthetic target of nanoscale atomically precise catalysts because their resulting structure, stereochemistry and tacticity has profound impact on their properties (crystalline vs amorphous) and provides a readout of the catalytic mechanism. Polymer synthesis also serves as an example of “atomically precise manufacturing” where atomically precise nanoscale catalysts construct polymers with atomic precision at increasing length scales.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

FETs Based on Doped Polyaniline/Polyethylene Oxide Fibers

A family of experimental highly miniaturized field-effect transistors (FETs) is based on exploitation of the electrical properties of nanofibers of polyaniline/ polyethylene oxide (PANi/PEO) doped with camphorsulfonic acid. These polymer-based FETs have the potential for becoming building blocks of relatively inexpensive, low-voltage, highspeed logic circuits that could supplant complementary metal oxide/semiconductor (CMOS) logic circuits. The development of these polymerbased FETs offers advantages over the competing development of FETs based on carbon nanotubes. Whereas it is difficult to control the molecular structures and, hence, the electrical properties of carbon nanotubes, it is easy to tailor the electrical properties of these polymerbased FETs, throughout the range from insulating through semiconducting to metallic, through choices of doping levels and chemical manipulation of polymer side chains. A further advantage of doped PANi/PEO nanofibers is that they can be made to draw very small currents and operate at low voltage levels, and thus are promising for applications in which there are requirements to use many FETs to obtain large computational capabilities while minimizing power demands. Fabrication of an experimental FET in this family begins with the preparation of a substrate as follows: A layer of silicon dioxide between 50 and 200 nm thick is deposited on a highly doped (resistivity 0.01 W.cm) silicon substrate, then gold electrodes/contact stripes are deposited on the oxide. Next, one or more fibers of camphorsulphonic acid-doped PANi/PEO having diameters of the order of 100 nm are electrospun onto the substrate so as to span the gap between the gold electrodes (see Figure 1). Figure 2 depicts measured current-versus-voltage characteristics of the device of Figure 1, showing that saturation channel currents occur at source-todrain potentials that are surprisingly low, relative to those of CMOS FETs. The hole mobility in the depletion regime in this transistor was found to be 1.4 10(exp -4) sq cm/(V.s), while the one-dimensional charge density at zero gate bias was estimated to be approximately one hole per 50 two-ring repeat units of polyaniline, consistent with the rather high channel conductivity (approx. 10(exp -3) S/cm). Reducing or eliminating the PEO content of the fibers is expected to enhance the properties of future versions of this transistor.

Theofylaktos, Noulie↗

Mechanical, Morphological, and Charge Transport Properties of NDI Polymers with Variable Built‐in Π‐Conjugation Lengths Probed by Simulation and Experiment

Abstract Mechanically deformable polymeric semiconductors are a key material for fabricating flexible organic thin‐film transistors (FOTFTs)—the building block of electronic circuits and wearable electronic devices. However, for many π‐conjugated polymers achieving mechanical deformability and efficient charge transport remains challenging. Here the effects of polymer backbone bending stiffness and film microstructure on mechanical flexibility and charge transport are investigated via experimental and computational methods for a series of electron‐transporting naphthalene diimide (NDI) polymers having differing extents of π‐conjugation. The results show that replacing increasing amounts of the π‐conjugated comonomer dithienylvinylene (TVT) with the π‐nonconjugated comonomer dithienylethane (TET) in the backbone of the fully π‐conjugated polymeric semiconductor, PNDI‐TVT 100 (yielding polymeric series PNDI‐TVT x , 100 ≥x≥ 0), lowers backbone rigidity, degree of texturing, and π–π stacking interactions between NDI moieties. Importantly, this comonomer substitution increases the mechanical robustness of PNDI‐TVT x while retaining efficient charge transport. Thus, reducing the TVT content of PNDI‐TVT x suppresses film crack formation and dramatically stabilizes the field‐effect electron mobility upon bending (e.g., 2 mm over 2000 bending cycles). This work provides a route to tune π–π stacking in π‐conjugated polymers while simultaneously promoting mechanical flexibility and retaining good carrier mobility in FOTFTs.

Chemistry↗

Exploring Microphase Separation in Semi-Fluorinated Diblock Copolymers: A Combined Experimental and Modeling Investigation

We report the combined experimental and theoretical study of the bulk self-assembly behavior of polystyrene-blockpoly( 2,3,4,5,6-pentafluorostyrene) diblock copolymers. These block copolymers were designed to create highly antagonistic blocks (with a high Flory−Huggins interaction parameter, χ) with minimum disruption to the molecular construct (i.e., only replacing five hydrogen atoms with five fluorine atoms). A large library of diblock copolymers (41 samples) was synthesized by reversible addition− fragmentation chain transfer (RAFT) polymerization to map out a major portion of the phase space. All block copolymers exhibited narrow molecular weight distributions with dispersity (D) values between 1.07 and 1.32, and subsequent thermal annealing revealed phase separation into well-defined nanoscale morphologies depending on their molecular composition, as determined from small-angle X-ray scattering and transmission electron microscopy analyses, with an experimental phase diagram being constructed. The χ value at 25 °C for this block copolymer was estimated to be 0.2 using strong segregation theory, based on trends in phase-separated domain spacing and interfacial width. When applying theoretical approaches, the majority of the domain spacing data trends were captured by a coil−coil diblock copolymer model; however, a better fit to the data for samples with shorter fluorinated blocks was obtained with a rod−coil model, indicating that the chains in these fluorinated blocks likely have a higher inherent stiffness and were thus rod-like. This observation demonstrates that, due to the very high value of χ, a transition from coil−coil to rod−coil behavior can be obtained purely by reducing the length of the stiffer of the two blocks and without varying temperature or the chemical composition of the polymers. Here, this work showcases the presence of strong microphase separation within AB diblock copolymers despite the relatively similar chemical composition of the constituent “A” and “B” units, with a clear transition from rod−coil to coil−coil segregation behavior.

RAFT polymerization↗

Tunable Nanoscale Structure via Divalent Ion Identity in Charged-Neutral Polymer Blends

Charged-neutral polymer blends, wherein an ioncontaining polymer is blended with a neutral polymer, are potential candidates for battery electrolytes due to their improved ion transport properties and electrochemical stability. Though electrostatic interactions in charged polymer blends can theoretically stabilize ordered nanostructures analogous to those observed in neutral block copolymers, direct experimental evidence remains limited. Here, we investigate the effects of divalent cation identity on the nanoscale morphology of charged-neutral polymer blends composed of poly(ethylene oxide) (PEO) and Mg 2+ or Ca 2+ ioncontaining polymers, poly[3-(methylacryloxy)propylsulfonyl-1-(trifluoromethanesulfonylimide)] (P(Mg(MTFSI) 2 ) or P(Ca- (MTFSI) 2 ). By tuning the size of the divalent counterion, we are able to precisely tune the ion solvation between the free cation and PEO, which acts as a solvent in this system. Differential scanning calorimetry (DSC) and small-angle X-ray scattering (SAXS) measurements reveal that Mg 2+ and Ca 2+ ions induce distinct structural behavior. In both systems, the blends become more miscible as the concentration of ion-containing polymer is increased indicated by increased suppression of PEO crystallinity. At the highest concentrations of P(Mg(MTFSI) 2 ), the blends undergo microphase separation and generate nanostructures with shortranged ordering. In contrast, calcium ions, which are more readily solvated by PEO, produce more homogeneous blends characterized by a single glass-transition temperature and featureless SAXS data. The results demonstrate the novel experimental confirmation that charged-neutral polymer blends can undergo microphase separation and show that counterion identity can be exploited as a design parameter to control nanoscale morphology.

Ions↗

AI‐Accelerated Optimization of Self‐Assembled Organic Mixed Ionic‐Electronic Conductors (OMIEC) (Final Report)

This document describes research activities, products and outcomes of a DOE-funded program to help accelerate development of Organic Mixed Ionic Electronic Conductors (OMIECs) using neutron scattering and high-throughput experimentation. OMIECs are organic materials that conduct both ionic and electronic charge carriers. For these new OMIEC materials, self-assembling ion-conducting block copolymers (BCPs) are used as a structural template for electronic conducting polymers. This forms OMIECs with long-range structural order that can help facilitate long-range electronic transport. The conductive properties of OMIECs are closely associated with their structure, which is affected by solution conditions and polymer macromolecular designs. Thus high-throughput experimentation has been implemented to explore this large design space effectively. The BCP-CP OMIEC systems explored are composed of ion-conducting diblock or triblock copolymers containing polyethylene oxide (PEO), di(ethylene glycol) ethyl ether acrylate (DEGEEA) or poly(ethylene glycol) methyl ether acrylate) (PEGMEA) hydrophilic blocks. These blocks will be coupled with either polypropylene oxide (PPO) or polyheptafluorobutyl acrylate (PHFBA) hydrophobic blocks to drive assembly. The electronic conducting component consists of several different types of conjugated polymers. Small angle scattering of neutrons and X-rays (SANS/SAXS) as well as electrochemical analysis have been coupled with modern algorithms for autonomous research using artificial intelligence (AI).

36 MATERIALS SCIENCE↗