Our aim was to decipher potential synergy between phosphorus-nitrogen (PN) and silicon (Si) in flame-retardant (FR) coatings for cotton textiles using a novel TRIAMO-based phosphoramidate-FR (TD) as a benchmark. For that we chose a comparative approach, employing a silica-free diethylenetriamine based derivative (DD), a dual-layer coating of tetraethyl orthosilicate (TEOS) and DD (DD/T). Standardized flame tests revealed that TD exhibited reduced performance at low add-on compared to DD, while DD/T consistently showed improved performance across loadings. TG-IR studies demonstrated that phosphoramidate species degrade via the release of triethyl phosphate (TEP) into the gas phase while forming PN networks on the substrate, independent of silica presence. However, functionalized silane networks accelerate the condensed phase mechanism of TEP by limiting gas diffusion. This was evidenced by XPS as TD yields a dense network of aliphatic PNO species such as phosphoramides and phosphor oxynitrides, while DD predominantly forms phosphazenes. These findings align with isoconversional kinetic studies showing higher activation energies for TD-treated cotton, attributed to diffusion limitations induced by the sol-gel network. This barrier effect also inhibits cotton pyrolysis, and enhances the structural integrity of char, as evidenced by SEM, DSC, and DTG data. While TEOS in DD/T alone does not alter the FR mechanism, it synergistically enhances char formation without impeding dehydration activity. In contrast, functionalized silanes demonstrate synergy only at critical add-ons; at lower loadings, the barrier effect disrupts the interaction between the FR moiety and the substrate. These findings suggest that the passivation and barrier effects of silica networks, though beneficial, may be overestimated in functionalized silane coatings for reactive substrates like cotton, emphasizing the need for increased loading levels to achieve desired FR performance. The same conclusion was found for functionalized phosphonate (DPTS) and amine-based silanes (TRI-AMO), demonstrating that our findings are applicable for systems beyond phosphoramidate.
A concept to prepare a highly hydrophobic composite with self-healing properties has been designed and verified. The new material is based on a composite of a crystalline hydrophobic fluoro wax, synthesized from montan waxes and perfluoroethylene alcohols, combined with spherical silica nanoparticles equipped with a hydrophobic shell. Highly repellent layers were prepared using this combination of a hydrophobic crystalline wax and silica nanoparticles. The novel aspect of our concept was to prepare a ladder-like structure of the hydrophobic shell allowing the inclusion of a certain share of wax molecules. Wax molecules trapped in the hydrophobic structure during mixing are hindered from crystallizing; therefore, these molecules maintain a higher mobility compared to crystallized molecules. When a thin layer of the composite material is mechanically damaged, the mobile wax molecules can migrate and heal the defects to a certain extent. The general preparation of the composite is described and XRD analysis demonstrated that a certain share of wax molecules in the composite are hindered to crystallize. Furthermore, we show that the resulting material can recovery its repellent properties after surface damage.
Thin, flat textile roofing offers negligible heat insulation. In warm areas, such roofing membranes are therefore equipped with metallized surfaces to reflect solar heat radiation, thus reducing the warming inside a textile building. Heat reflection effects achieved by metallic coatings are always accompanied by shading effects as the metals are non-transparent for visible light (VIS). Transparent conductive oxides (TCOs) are transparent for VIS and are able to reflect heat radiation in the infrared. TCOs are, e.g., widely used in the display industry. To achieve the perfect coatings needed for electronic devices, these are commonly applied using costly vacuum processes at high temperatures. Vacuum processes, on account of the high costs involved and high processing temperatures, are obstructive for an application involving textiles. Accepting that heat-reflecting textile membranes demand less perfect coatings, a wet chemical approach has been followed here when producing transparent heat-reflecting coatings. Commercially available TCOs were employed as colloidal dispersions or nanopowders to prepare sol–gel-based coating systems. Such coatings were applied to textile membranes as used for architectural textiles using simple coating techniques and at moderate curing temperatures not exceeding 130 °C. The coatings achieved about 90% transmission in the VIS spectrum and reduced near-infrared transmission (at about 2.5 µm) to nearly zero while reflecting up to 25% of that radiation. Up to 35% reflection has been realized in the far infrared, and emissivity values down to ε = 0.5777 have been measured.
Der pH-Wert der menschlichen Haut liegt nicht im neutralen Bereich, sondern ist mit Werten von 3,5-6 - je nach Körperstelle - leicht sauer. Dies bietet der kommensalen Hautflora einen geeigneten Lebensraum, wirkt jedoch abtötend auf einige pathogene Mikroorganismen und inaktivierend auf einige Viren. Dieser Säureschutzmantel der Haut stellt somit eine erste äußere Schutzschicht vor dem Befall von Krankheitserregern dar. Ein entsprechender Oberflächen-pH-Wert auf Textilien kann dazu beitragen, die Übertragung von Krankheitserregern durch die Kleidung von Mitarbeitern im Ge-sundheitswesen zu minimieren und gleichzeitig keinen negativen Einfluss auf die hauteigene Flora auszuüben. Zudem kann die Besiedlung von z.B. Bettwäsche durch pathogene Mikroorganismen vermindert werden. Einen positiven Einfluss kann dies zudem auf die bakterienassoziierte Geruchsbildung auf Funktionskleidung haben.
Polyester fibers are widely employed in a multitude of sectors and applications from the technical textiles to everyday life thanks to their durability, strength, and flexibility. Despite these advantages, polyester lacks in dyeability, adhesion of coating, hydrophilicity, and it is characterized by a low wettability respect to natural fibers. On this regard, beyond the harmful hydrophobic textile finishings of polyester fabrics containing fluorine-compounds, and in order to avoid pre-treatments, such as laser irradiation to improve their surface properties, research is moving towards the development of fluorine-free and safer coatings. In this work, the (3-glycidyloxypropyl)trimethoxysilane (GPTMS) and various long alkyl-chain alkoxysilanes were employed for the fabrication in the presence of a catalyst of a water-based superhydrophobic finishing for polyester fabrics with a simple sol-gel, non-fluorinated, sustainable approach and the dip-pad-dry-cure method. The finished polyester fabrics surface properties were investigated by static and dynamic water repellency tests. Additionally, the resistance to common water-based liquids, abrasion resistance, moisture adsorption, and air permeability measurements were performed. Scanning electron microscopy was employed to examine the micro- and nano-morphology of the functionalized polyester fabrics surfaces. The obtained superhydrophobic finishings displayed high water-based stain resistance as well as good hydrophobicity after different cycles of abrasion.
In the present study, DOPO-based alkoxysilane (DOPO-ETES) and amido alkoxysilane (DOPO-AmdPTES) were synthesized by one-step and without by-products as halogen-free flame retardants. The flame retardants were applied on cotton fabric utilizing sol–gel method and pad-dry-cure finishing process. The flame retardancy, the thermal stability and the combustion ehaviour of treated cotton were evaluated by surface and bottom edge ignition flame test (according to EN ISO 15025), thermogravimetric analysis (TGA) and micro-scale combustion calorimeter (MCC). Unlike CO/DOPO-ETES sample, cotton treated with DOPO-AmdPTES nanosols exhibits self-extinguishing ehaviour with high char residue, an improvement of the LOI value and a significant reduction of the PHRR, HRC and THR compared to pristine cotton. Cotton finished with DOPO-AmdPTES reveals a semi-durability after ten laundering cycles keeping the flame-retardant properties unchanged. According to the results obtained from TGA-FTIR, Py-GC/MS and XPS, the major activity of flame retardant occurs in the condensed phase via catalytic induced char formation as physical barrier along with the activity in the gas phase derived mainly from the dilution effect. The early degradation of CO/DOPO-AmdPTES compared to CO/DOPO-ETES, triggered by the cleavage of the weak bond between P and C=O, as the DFT study indicated, provides the beneficial effect of this flame retardant on the fire resistance of cellulose. Graphical abstract
Schweißerschutzkleidung muss unterschiedlichen Anforderungen genügen. Sie muss u.a. flammfest sein, den Schweißer vor Metallspritzern schützen, die beim Schweißen entstehen, und einen Schutz vor UV-Licht sicherstellen, das im Schweißbogen entsteht. Besonders der Schutz vor Metallspritzern wird durch das Flächengewicht der Textilien bestimmt. Der entsprechende Schutzfaktor wird durch Tropfen aus flüssigem Eisen bestimmt, die auf ein Gewebe fallen. Dabei gilt: Je höher das Flächengewicht ausfällt, desto höher ist der Schutz vor Schweißspritzern. Jedoch gilt auch: Je höher das Flächengewicht ausfällt, desto schlechter ist der Tragekomfort und desto wärmender ist die Kleidung, wodurch die körperliche Belastung des Trägers steigt. Durch die Applikation von Nanopartikeln ist es möglich, das benötigte Flächengewicht der Kleidung zu reduzieren.
Die Anforderungen an Textilien unterscheiden sich je nach Anwendungsbereich stark, wobei es häufig nicht bei nur einer benötigten Funktionalität bleibt. Im Bereich der Funktions- oder Schutzkleidung bzw. PSA ist es z.B. nötig, die Träger der Kleidung vor UV-Strahlung zu schützen. Gleichzeitig bieten hier selbstreinigende Effekte gewisse Vorteile. Zudem kann eine antimikrobielle Wirkung im Bereich der Funktionskleidung die Bildung unangenehmer Gerüche vermindern, sowie im Bereich der PSA – besonders im Gesundheitswesen – zur Unterbrechung von Infektionsketten beitragen. Eine Möglichkeit, diese 3 gewünschten Funktionen in nur einem Ausrüstungsschritt zu erzielen, ist die Immobilisierung von Titandioxid (TiO2). Dieses wird aber aufgrund einer REACH-Listung kritisch für die Anwendung im textilen Sektor gesehen. Nachteilig ist zudem, dass es seine Wirkung nur unter UV-Einstrahlung entfaltet und damit nicht für den Innenbereich geeignet ist. Alternativ können Photokatalysatoren wie dotierte Zinkoxide (ZnO) verwendet werden, die auch durch Einstrahlung im Bereich des sichtbaren Lichts eine katalytische Aktivität aufweisen, die zur Abtötung von Mikroorganismen und zum Abbau organischer Verschmutzungen führen kann.
In the IGF project No. 19617 N, nitrogen and phosphorous substituted alkoxysilanes were prepared and their ability to inhibit fire growth and spread for fabrics was explored. To this end, a series of flame retardants were synthesized using different strategies including click chemistry and nucleophilic substitution of commercial organophosphorus compounds with amino-based trialkoxysilanes and/or cyanuric chloride. The new halogen-free and aldehyde-free flame retardants were applied to different fabrics such as cotton (CO), polyethylene terephthalate (PET), polyamide (PA) and their blends using the well-known pad-dry-cure technique and sol-gel method. The flame-retarding efficiencies were evaluated by EN ISO 15025 test methods (protective clothing-protection against heat and flame method of test for limited flame spread). Good flame retardancy of the hybrid organic-inorganic materials was achieved with the addition of as small amount as 3-5 wt.% for cotton fabrics. Moreover, the water solubility and the washing resistance could be controlled through the functional groups attached to the phosphor atom or through the optimization of the curing temperature. Overall, the research project demonstrated that N-P-silanes are very good permanent flame retardants for textiles.
The textile-finishing industry, is one of the main sources of persistent organic pollutants in water; in this regard, it is necessary to develop and employ new sustainable approaches for fabric finishing and treatment. This research study shows the development of an efficient and eco-friendly procedure to form highly hydrophobic surfaces on cotton fabrics using different modified silica sols. In particular, the formation of highly hydrophobic surfaces on cotton fabrics was studied by using a two-step treatment procedure, i.e., first applying a hybrid silica sol obtained by hydrolysis and subsequent condensation of (3-Glycidyloxypropyl)trimethoxy silane with different alkyl(trialkoxy)silane under acid conditions, and then applying hydrolyzed hexadecyltrimethoxysilane on the treated fabrics to further improve the fabrics' hydrophobicity. The treated cotton fabrics showed excellent water repellency with a water contact angle above 150° under optimum treatment conditions. The cooperative action of rough surface structure due to the silica sol nanoparticles and the low surface energy caused by long-chain alkyl(trialkoxy)silane in the nanocomposite coating, combined with the expected roughness on microscale due to the fabrics and fiber structure, provided the treated cotton fabrics with excellent, almost super, hydrophobicity and water-based stain resistance in an eco-sustainable way.
Nanocoatings based on sol–gel coatings are presented as suitable tool to modify materials based on polymers. The main focus is set onto textiles as the most common polymer materials. It presents which types of functionalization can be reached by modified sol–gel processes. Also a suitable categorization of functions is given and set into relation to common applications. A special focus is set on the functional properties, antimicrobial, UV protective, and flame retardant. The concept of bifunctional coatings is discussed and especially the combination of water-repellent and antistatic is presented.
Das textile Bauen ist ein seit vielen Jahren wachsender Bereich der Textilindustrie. Durch die Verwendung textiler Materialien bieten sich nicht zuletzt fur die Architektur neue gestalterische Moglichkeiten, die mit konventionellen Baumaterialien nicht realisierbar sind. Bekannte Beispiele fur textile Bauwerke sind grose Sportarenen, Bahnhofe und Flughafen. Dabei sind Leichtbauweisen und zumindest teilweise Transparenz der Bauwerke auf einer Seite herausragende Eigenschaften, auf der anderen Seite stellen diese Gebaude besondere Anforderungen an das Klima- und Energiemanagement. Der Innenraum kann sich bei Sonneneinstrahlung stark aufheizen, da neben dem sichtbaren Licht vor allem ein Grosteil des Infrarotanteils der solaren Strahlung transmittieren kann. Im konventionellen Bauen existieren bereits hohe Anforderungen an die energietechnische Ausgestaltung von Bauwerken, die u.a. uber eine effiziente Warmedammung erfullt werden. Dies wird in der Regel mit Hilfe von voluminosen, offenporigen Dammstoffen erreicht. Ziel ist es dabei vornehmlich, den Verlust von Warme aus dem Innenraum zu verringern, gleichzeitig konnen schlecht warmeleitende Stoffe bei hoher Masse und hoher spezifischer Warmekapazitat Temperaturspitzen im Sommer abpuffern. Auch fur das textile Bauen ist die Energieeffizienz ein wichtiger Aspekt. Die Verwendung von schweren Dammstoffen widerspricht dabei aber der Idee der flexiblen textilen Leichtbauweise.
Energy consumption by air-conditioning is expansive and leads to the emission of millions of tons of CO2 every year. A promising approach to circumvent this problem is the reflection of solar radiation: Rooms that would not heat up by irradiation will not need to be cooled down. Especially, transparent conductive metal oxides exhibit high infrared (IR) reflectivity and are commonly applied as low-emissivity coatings (low-e coatings). Indium tin oxide (ITO) coatings are the state-of-the-art application, though indium is a rare and expensive resource. This work demonstrates that aluminum-doped zinc oxide (AZO) can be a suitable alternative to ITO for IR-reflection applications. AZO synthesized here exhibits better emissivity to be used as roofing membrane coatings for buildings in comparison to commercially available ITO coatings. AZO particles forming the reflective coating are generated via solvothermal synthesis routes and obtain high conductivity and IR reflectivity without the need of any further post-thermal treatment. Different synthesis parameters were studied, and their effects on both conductive and optical properties of the AZO nanoparticles were evaluated. To this end, a series of characterization methods, especially 27Al-nuclear magnetic resonance spectroscopy (27Al-NMR) analysis, have been conducted for a deeper insight into the particles' structure to understand the differences in conductivity and optical properties. The optimized AZO nanoparticles were coated on flexible transparent textile-based roofing membranes and tested as low-e coatings. The membranes demonstrated higher thermal reflectance compared with commercial ITO materials with an emissivity value lowered by 16%.
Im IGF-Projekt Nr. 19617 N wurden stickstoff- und phosphorsubstituierte Alkoxysilane hergestellt und ihre flammhemmenden Eigenschaften für Textilien untersucht. Die Synthesen erfolgten nach unterschiedlichen Strategien wie der Klick-Chemie und der nukleophilen Substitution kommerziell erhältlicher Organophosphorverbindungen mit aminobasierten Trialkoxysilanen und/oder Cyanurchlorid. Diese neuartigen, halogen- und aldehydfreien Flammschutzmittel wurden auf Stoffe aus Baumwolle (BW), Polyethylenterephthalat (PET), Polyamid (PA), sowie Mischgeweben daraus mit der industriell etablierten Pad-Dry-Cure-Technik und mittels Sol-Gel-Verfahren aufgetragen. Die flammhemmenden Eigenschaften wurden mit den Prüfverfahren nach EN ISO 15025 (Schutzkleidung – Schutz gegen Hitze und Flammprüfverfahren für begrenzte Flammenausbreitung) bewertet. Eine gute Schwerentflammbarkeit der hybriden organisch-anorganischen Materialien wurde bei einer geringen Menge von 3-5 Gew.-% auf Baumwollgeweben erreicht. Darüber hinaus konnten die Wasserlöslichkeit und die Waschbeständigkeit durch die an das Phosphoratom gebundenen funktionellen Gruppen und durch die Optimierung der Härtungstemperatur kontrolliert werden. Insgesamt zeigte das Forschungsprojekt, dass N-P-Silane sehr gute permanente Flammschutzmittel für Textilien sind.
Three established test methods employed for evaluating the abrasion or wear resistance of textile materials were compared to gain deeper insight into the specific damaging mechanisms to better understand a possible comparability of the results of the different tests. The knowledge of these mechanisms is necessary for a systematic development of finishing agents improving the wear resistance of textiles. Martindale, Schopper, and Einlehner tests were used to analyze two different fabrics made of natural (cotton) or synthetic (polyethylene terephthalate) fibers, respectively. Samples were investigated by digital microscopy and scanning electron microscopy to visualize the damage. Damage symptoms are compared and discussed with respect to differences in the damaging mechanisms.
Hauptziel des Projektes war zum einen die Entwicklung einer validen Testmethode auf Grundlage vorliegender Normen, welche die in der betrieblichen Praxis auftretende Degradation abreinigbarer Filtermedien (hohe Temperaturen, aggressive chemische Atmospharen) praxisnah abbilden kann. Die Methode sollte auch die mechanische Alterung der Medien durch Staubbeaufschlagung sowie Abreinigungs Druckstose berucksichtigen (DIN ISO 11057). Innerhalb des Projektes konnten umfangreiche Praxiserfahrungen mit der Inbetriebnahme und dem Betrieb einer schadgasbeaufschlagten, temperierbaren Testkammer zur chemischen Alterung von Filtermedien auf Grundlage der Vorgaben der DIN EN ISO 16891 gewonnen werden. Sollen vergleichbare Prufdaten fur mehrere Proben verlasslich ermittelt werden, sind bei den Untersuchungen demnach umfangreiche Randbedingungen zu beachten. Insbesondere zeigten die Untersuchungen den hohen technischen Aufwand zur Durchfuhrung der Filtertests auf, welche nicht zuletzt auch aufgrund der erforderlichen Sicherheitstechnik und langen Untersuchungsdauer eine Umsetzung insbesondere bei KMU aus wirtschaftlichen Grunden erschwert ist. Es konnte weiter dargestellt werden, dass die Kombination von chemisch-thermischer und mechanisch(-thermischer) Alterung durch den Einsatz verschiedener Prufeinrichtungen grundsatzlich umsetzbar ist. Die im Rahmen des Vorhabens entwickelte Testmethode einer chemischen Alterung der Filtermatrices durch Gasphasenexposition in einer Druckkammer ermoglicht kurzere Beanspruchungszeitraume bei reduziertem zu behandelnden Schadgasanfall und kann damit den wirtschaftlichen Betrieb eines entsprechenden Prufstandes ermoglichen. Kombiniert mit der externen mechanischen Alterung durch Staubbeaufschlagung und Moglichkeit der parallelen Temperaturaufpragung gem. EN ISO 16891 auf mehrere Filtermedien-Proben lasst sich das thermisch, chemisch und mechanisch induzierte Degradationsverhalten von Filtermedien ggf. realitatsnah und mit wirtschaftlich vertretbarem Aufwand in eine Prufvorschrift uberfuhren. Entsprechende Validierungsarbeiten sind Bestandteil eines aktuell gestarteten Folgeprojektes. Das zweite Hauptziel des Projektes war es Ausrustungen zu entwickeln, die zu einer verbesserten Bestandigkeit gegenuber aggressiven Komponenten fuhren. Die Ergebnisse zeigten, dass mit dem Sol-Gelverfahren mechanisch stabile Beschichtungen auf Faservlies dauerhaft aufgetragen werden konnten, welche insbesondere die chemisch induzierte Degradation von Aramiden reduzieren konnen. Bei Aramiden handelt es sich um relativ teure Hochleistungsmaterialien, von welchen bekannt ist, dass ihre Bestandigkeit sowohl gegen uber UV-Strahlung als auch unterschiedlichen Schadgasen gering ist. Daher stellen die Bestandigkeit der Materialien verbessernde Ausrustungen eine wichtige Entwicklung fur Unternehmen dar, um auf diese Weise bestandigere Aramid-basierte Produkte zu erhalten. Als besonders geeignet stellten sich dabei Fluorcarbonausrustungen, organisch-anorganische Hybride auf Basis von GPTMS und Zirkonium-haltige Ausrustungen heraus.
Indium tin oxide (ITO) particle coatings are known for high transparency in the visible, good conductive properties and near-infrared absorption. These properties depend on ITO particle's stoichiometric composition, defects and size. Here we present a method to gradually change ITO particle's optical properties by a simple and controlled laser irradiation process. The defined irradiation process and controlled energy dose input allows one to engineer the absorption and transmission of coatings made from these particles. We investigate the role of the surrounding solvent, influence of laser fluence and the specific energy dose targeting modification of the ITO particle's morphology and chemistry by stepwise laser irradiation in a free liquid jet. TEM, SEM, EDX, XPS, XRD and Raman are used to elucidate the structural, morphological and chemical changes of the laser-induced ITO particles. On the basis of these results the observed modification of the optical properties is tentatively attributed to chemical changes, e.g. laser-induced defects or partial reduction.
The wet chemical deposition of solution processed transparent conducting oxides (TCO) provides an alternative low cost and economical deposition technique to realize large-areas of conducting films. Since the price for the most common TCO Indium Tin Oxide rises enormously, Aluminum Zinc Oxide (AZO) as alternative TCO reaches more and more interest. The optoelectronical properties of nanoparticle coatings strongly depend beneath the porosity of the coating on the shape and size of the used particles. By using bigger or rod-shaped particles it is possible to minimize the amount of grain boundaries resulting in an improvement of the electrical properties, whereas particles bigger than 100 nm should not be used if highly transparent coatings are necessary as these big particles scatter the visible light and lower the transmittance of the coatings. In this work we present a simple method to synthesize AZO particles with different shape and size, but comparable electronical properties. We use a simple, well reproducible polyol method for synthesis and influence the shape and size of the particles by adding different amounts of water to the precursor solution. We can show that the addition of aluminum as dopant strongly hinders the crystal growth but the addition of water counteracts this, so that both, spherical and rod-shaped particles can be obtained.
Several ionic liquids are excellent solvents for cellulose. Starting from that finishing of PET fabrics with cellulose dissolved in ionic liquids like 1-ethyl-3-methyl imidazolium acetate, diethylphosphate and chloride, or the chloride of butyl-methyl imidazolium has been investigated. Finishing has been carried out from solutions of different concentrations, using microcrystalline cellulose or cotton and by employing different cross-linkers. Viscosity of solutions has been investigated for different ionic liquids, concentrations, cellulose sources, linkers and temperatures. Since ionic liquids exhibit no vapor pressure, simple pad-dry-cure processes are excluded. Before drying the ionic liquid has to be removed by a rinsing step. Accordingly rinsing with fresh ionic liquid followed by water or the direct rinsing with water have been tested. The amount of cellulose deposited has been investigated by gravimetry, zinc chloride iodine test as well as reactive dyeing. Results concerning wettability, water up-take, surface resistance, wear-resistance or washing stability are presented.