Communicating Supraparticles to Enable Perceptual, Information-Providing Matter.

Materials are the fundament of the physical world, whereas information and its exchange are the centerpieces of the digital world. Their fruitful synergy offers countless opportunities for realizing desired digital transformation processes in the physical world of materials. Yet, to date, a perfect connection between these worlds is missing. From the perspective, this can be achieved by overcoming the paradigm of considering materials as passive objects and turning them into perceptual, information-providing matter. This matter is capable of communicating associated digitally stored information, for example, its origin, fate, and material type as well as its intactness on demand. Herein, the concept of realizing perceptual, information-providing matter by integrating customizable (sub-)micrometer-sized communicating supraparticles (CSPs) is presented. They are assembled from individual nanoparticulate and/or (macro)molecular building blocks with spectrally differentiable signals that are either robust or stimuli-susceptible. Their combination yields functional signal characteristics that provide an identification signature and one or multiple stimuli-recorder features. This enables CSPs to communicate associated digital information on the tagged material and its encountered stimuli histories upon signal readout anywhere across its life cycle. Ultimately, CSPs link the materials and digital worlds with numerous use cases thereof, in particular fostering the transition into an age of sustainability.

Magnetic in situ determination of surface coordination motifs by utilizing the degree of particle agglomeration.

Most analytical techniques used to study the surface chemical properties of superparamagnetic iron oxide nanoparticles (SPIONs) are barely suitable for in situ investigations in liquids, where SPIONs are mostly applied for hyperthermia therapy, diagnostic biosensing, magnetic particle imaging or water purification. Magnetic particle spectroscopy (MPS) can resolve changes in magnetic interactions of SPIONs within seconds at ambient conditions. Herein, we show that by adding mono- and divalent cations to citric acid capped SPIONs, the degree of agglomeration can be utilized to study the selectivity of cations towards surface coordination motifs via MPS. A favored chelate agent, like ethylenediaminetetraacetic acid (EDTA) for divalent cations, removes cations from coordination sites on the SPION surface and causes redispersion of agglomerates. The magnetic determination thereof represents what we call a "magnetically indicated complexometric titration". The relevance of agglomerate sizes for the MPS signal response is studied on a model system of SPIONs and the surfactant cetrimonium bromide (CTAB). Analytical ultracentrifugation (AUC) and cryogenic transmission electron microscopy (cryo-TEM) reveal that large micron-sized agglomerates are required to significantly change the MPS signal response. With this work, a fast and easy-to-use characterization method to determine surface coordination motifs of magnetic nanoparticles in optically dense media is demonstrated.

Magnetizing Polymer Particles with a Solvent-Free Single Stage Process Using Superparamagnetic Iron Oxide Nanoparticles (SPION)s.

Magnetic polymer composites are used in a variety of applications in many industries. Their production methods are usually time-consuming and solvent-intensive as they are performed in liquid phase processes, such as emulsion polymerization or precipitation. In this work, a quick, easy, and solvent-free method is presented to coat polymer particles with a discrete, non-coherent coating of superparamagnetic nanoparticles. The results of the dry coating process are evaluated optically, by means of scanning electron microscopy (SEM), via powder X-ray diffraction and thermally by means of differential scanning calorimetry, before finally demonstrating the effectiveness of dry coating by means of a vibrating sample magnetometer.

Recording Temperature with Magnetic Supraparticles.

Small-sized temperature indicator additives autonomously record temperature events via a gradual irreversible signal change. This permits, for instance, the indication of possible cold-chain breaches or failure of electronics but also curing of glues. Thus, information about the materials' thermal history can be obtained upon signal detection at every point of interest. In this work, maximum-temperature indicators with magnetic readout based on micrometer-sized supraparticles (SPs) are introduced. The magnetic signal transduction is, by nature, independent of the materials' optical properties. This facilitates the determination of valuable temperature information from the inside, that is, the bulk, even of dark and opaque macroscopic objects, which might differ from their surface. Compared to state-of-the-art optical temperature indicators, complementary magnetic readout characteristics ultimately expand their applicability. The conceptualized SPs are hierarchically structured assemblies of environmentally friendly, inexpensive iron oxide nanoparticles and thermoplastic polymer. Irreversible structural changes, induced by polymer softening, yield magnetic interaction changes within and between the hierarchic sub-structures, which are distinguishable and define the temperature indication mechanism. The fundamental understanding of the SPs' working principle enables customization of the particles' working range, response time, and sensitivity, using a toolbox-like manufacturing approach. The magnetic signal change is detected self-referenced, fast, and contactless.

Optically Sensitive and Magnetically Identifiable Supraparticles as Indicators of Surface Abrasion.

Identifying and ensuring the integrity of products plays an important role in today's globalized world. Miniaturized information taggants in the packaging surface are therefore required to monitor the product itself instead of applying external labels. Ideally, multiple types of information are stored in such additives. In this work, micrometer-sized core-shell particles (supraparticles) were developed to provide material surfaces with both an identifier and a surface abrasion indication functionality. The core of the supraparticles contains iron oxide nanoparticles that allow identification of the surface with a spectral magnetic code resolved by magnetic particle spectroscopy. The fluorescent silica nanoparticles in the supraparticle shell can be abraded by mechanical stress and resolved by fluorescence spectroscopy. This provides information about the mechanical integrity of the system. The application as surfaces, that contain several types of information in one supraparticle, was demonstrated here by incorporating such bifunctional supraparticles as additives in a surface coating.

Colorful Luminescent Magnetic Supraparticles: Expanding the Applicability, Information Capacity, and Security of Micrometer-Scaled Identification Taggants by Dual-Spectral Encoding.

(Sub)micrometer-scaled identification (ID) taggants enable direct identification of arbitrary goods, thereby opening up application fields based on the possibility of tracking, tracing, and anti-counterfeiting. Due to their small dimensions, these taggants can equip in principle even the smallest subcomponents or raw materials with information. To achieve the demanded applicability, the mostly used optically encoded ID taggants must be further improved. Here, micrometer-scaled supraparticles with spectrally encoded luminescent and magnetically encoded signal characteristics are reported. They are produced in a readily customizable bottom-up fabrication procedure that enables precise adjustment of luminescent and magnetic properties on multiple hierarchy levels. The incorporation of commonly used magnetic nanoparticles and fluorescent dyes, respectively, into polymer nanocomposite particles, establishes a convenient toolbox of magnetic and luminescent building blocks. The subsequent assembly of selected building blocks in the desired ratios into supraparticles grants for all the flexibility to freely adjust both signal characteristics. The obtained spectrally resolved visible luminescent and invisible magnetic ID signatures are complementary in nature, thus expanding applicability and information security compared to recently reported optical- or magnetic-encoded taggants. Additionally, the introduced ID taggant supraparticles can significantly enhance the coding capacity. Therefore, the introduced supraparticles are considered as next-generation ID taggants.

Spray-Drying and Atomic Layer Deposition: Complementary Tools toward Fully Orthogonal Control of Bulk Composition and Surface Identity of Multifunctional Supraparticles.

Spray-drying is a scalable process enabling one to assemble freely chosen nanoparticles into supraparticles. Atomic layer deposition (ALD) allows for controlled thin film deposition of a vast variety of materials including exotic ones that can hardly be synthesized by wet chemical methods. The properties of coated supraparticles are defined not only by the nanoparticle material chosen and the nanostructure adjusted during spray-drying but also by surface functionalities modified by ALD, if ALD is capable of modifying not only the outer surfaces but also surfaces buried inside the porous supraparticle. Simultaneously, surface accessibility in the porous supraparticles must be ensured to make use of all functionalized surfaces. In this work, iron oxide supraparticles are utilized as a model substrate as their magnetic properties enable the use of advanced magnetic characterization methods. Detailed information about the structural evolution upon individual ALD cycles of aluminium oxide, zinc oxide and titanium dioxide are thereby revealed and confirmed by gas sorption analyses. This demonstrates a powerful and versatile approach to freely designing the functionality of future materials by combination of spray-drying and ALD.

A Single Magnetic Particle with Nearly Unlimited Encoding Options.

Communicating objects are demanded for product security and the concepts of a circular economy or the Internet of Nano Things. Smart additives in the form of particles can be the key to equip objects with the desired materials intelligence as their miniaturized size improves applicability and security. Beyond their proposed identification by optical signals, magnetic signals deriving from magnetic particles can hypothetically be used for identification but are to date only resolved roughly. Herein, a magnetic particle-based toolbox is reported, that provides more than 77 billion (77 × 109 ) different magnetic codes, adjustable in one single particle, that can be read out unambiguously, easily, and quickly. The key towards achieving the vast code variety is a hierarchical supraparticle design that is inspired by music: similarly to how the line-up variation of a musical ensemble yields distinguishable overtones, the variation of the supraparticle composition alters their magnetic overtones. By minimizing magnetic interactions, customizable signals are spectrally decoded by the simple method of magnetic particle spectroscopy. A large number of chemically adjustable magnetic codes and the possibility of their remote, contactless detection from within materials is a breakthrough for unexploited labeling applications and pave the way towards materials intelligence.

Reversible magnetism switching of iron oxide nanoparticle dispersions by controlled agglomeration.

The controlled agglomeration of superparamagnetic iron oxide nanoparticles (SPIONs) was used to rapidly switch their magnetic properties. Small-angle X-ray scattering (SAXS) and dynamic light scattering showed that tailored iron oxide nanoparticles with phase-changing organic ligand shells agglomerate at temperatures between 5 °C and 20 °C. We observed the concurrent change in magnetic properties using magnetic particle spectroscopy (MPS) with a temporal resolution on the order of seconds and found reversible switching of magnetic properties of SPIONs by changing their agglomeration state. The non-linear correlation between magnetization amplitude from MPS and agglomeration degree from SAXS data indicated that the agglomerates' size distribution affected magnetic properties.

Anodes for Li-ion batteries prepared from microcrystalline silicon and enabled by binder's chemistry and pseudo-self-healing.

Silicon, while suffering from major degradation issues, has been recognized as a next promising material to replace currently used graphite in the anodes of Li-ion batteries. Several pathways to mitigate the capacity fading of silicon has been proposed, including optimization of the electrode composition. Within the present work we evaluated different binder formulations to improve the long-term performance of the Li-ion batteries' anodes based on industrial grade silicon (Si) which is typically characterized by a particle sizes ranging from 100 nm to 5.5 microns. The decrease of pH in a binder formulation was found to detrimental for the cycling performance of Si due to enhanced formation of an ester-type bonding between the carboxylic group of the binder and hydroxyl group on the Si surface as well as cross-linking. Furthermore, the present work was focused on the use of the industrial grade Si with very high loading of Si material (up to 80% by weight) to better highlight the effects of the surface chemistry of Si and its influence on the performance of Si-based anodes in Li-ion batteries. The tested system allowed to establish a pseudo self-healing effect that manifests itself through the restoration of the anode capacity by approximately 25% and initiates after approximately 20 cycles. The stabilization of the capacity is attributed to self-limiting lithiation process. Such effect is closely related to SEI formation and transport properties of an electrode prepared from silicon of industrial grade.