Extracellular Polymeric Substances (EPS) are ubiquitous in biological wastewater treatment (WWT) technologies like activated sludge systems, biofilm reactors, and granular sludge systems. EPS recovery from sludge potentially offers a high-value material for the industry. It can be utilized as a coating in slow-release fertilizers, as a bio-stimulant, as a binding agent in building materials, for the production of flame retarding materials, and more. P recovered within the extracted EPS is an intrinsic part of the recovered material that potentially influences its properties and industrial applications. P is present in EPS in different speciation (e.g., P esters, poly-P, ortho-P, etc.). Such P species are already intensively used in the chemical industry to enhance thermal stability, viscoelasticity, emulsification, water-holding capacity, and many other properties of some natural and petroleum-derived polymers. The translation of this knowledge to EPS is missing which prevents the full utilization of phosphorus in EPS. This knowledge could allow us to engineer EPS via phosphorus for specific target properties and applications. In this review, we discuss how P could affect EPS properties based on experiences from other industries and reflect on how these P species could be influenced during the EPS extraction process or in the WWTPs.

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Micropatterned surfaces with both hydrophilic and hydrophobic regions are relevant for a wide range of applications from fuel cells to water harvesting systems. The preferential nucleation of water on hydrophilic regions can also be used to control frost nucleation on chemically patterned surfaces. So far, this concept has been tested on brittle silicon surfaces with only a few different sizes and shapes of hydrophilic regions. In this work, the concept of controlled icing is investigated on five polymeric surfaces with different surface energies modified by micropatterning them with three types of hydrophilic polymer brushes. Frost formation and propagation on the resulting patterned surfaces with regions of varying wettability is monitored and quantified using high-resolution thermal imaging. The study proves that control over frost nucleation and propagation using regions of varying wettability can be achieved on commodity polymers. In addition to influencing the time and location of ice nucleation, the local patterning affects the freezing propagation mode and rate due to its impact on the continuity and thickness of molecular water layers (MWL). These results show that local control over the state of MWLs is key to controlling both ice nucleation and propagation of freezing events on surfaces.

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Ultrasound is widely used in medical imaging, and emerging photo-acoustic imaging is crucial for disease diagnosis. Currently, high-end photo-acoustic imaging systems rely on piezo-electric materials for detecting ultrasound waves, which come with sensitivity, noise, and bandwidth limitations. Advanced applications demand a large matrix of broadband, high-resolution, and scalable ultrasound sensors. Silicon photonic circuits have been introduced to meet these requirements by detecting ultrasound-induced deformation and stress in silicon waveguides. Although higher sensitivities could facilitate the exploration of new applications, the high stiffness of the waveguide materials constrains the intrinsic sensitivity of the silicon photonic circuits to ultrasound signals. Here, we explore the impact of the mechanical properties of a polymer cladding on the sensitivity of silicon photonic ultrasound sensors. Our model and experiments reveal that optimizing the polymer cladding's stiffness enhances the resonance wavelength sensitivity. Experimentally, we show a fourfold increase in the sensitivity compared to the sensors without a cladding polymer and, a twofold sensitivity increase compared to the sensors with a cladding polymer of saturated cross-linking density. Interestingly, comparing experiments with the optomechanical model suggests that the change in Young's Modulus alone cannot explain the sensitivity increase. In conclusion, polymer-coated silicon photonic ultrasound sensors exhibit potential for advanced photo-acoustic imaging applications. It offers the prospect of increasing the ultrasound detection sensitivity of silicon photonic ultrasound sensors while using CMOS-compatible processes. This paves the way to integrate the polymer-coated silicon photonic ultrasound sensors with electronics to utilize the sensors in advanced medical imaging applications.

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A theoretical approach is presented to quantify the effect of ionic strength on the swelling and shrinkage of the hydrodynamic coil size of a generic biopolymer. This was conducted in view of extraction methods that often utilize acids and alkali combinations and, therefore, invariably impact the levels of salt found in commercially available biopolymers. This approach is supplemented by intrinsic viscosity measurements for the purpose of validation across a variety of biopolymer architectures, type of functionalization, as well as the quoted molar mass. By accurately capturing the magnitude of change in the coil size, it is discussed how a biopolymer coil size is far more sensitive to changes in the ionic strength than it is to the molar mass (or contour length) itself. In turn, it is highlighted why the current characterization strategies that make use of weight-averaged molar mass are prone to errors and cannot be used to establish structure—property relationships for biopolymers. As an alternative, the scope of developing an accurate understanding of coil sizes due to changes in the “soft” interactions is proposed, and it is recommended to use the coil size itself to highlight the underlying structure—property relationships.@en

In this work, we study the relationship between the molecular water layer (MWL) and frost freezing onset and propagation. The progression of frost has been reported to be governed by various localized icing phenomena, including interdroplet ice bridging, dry zones, and frost halos. Reports studying the state of water on surfaces have revealed the presence of a thin nanometer water layer on a range of surfaces. Regardless of further investigations that show environmental humidity, temperature, and surface energy to affect the thickness of the MWL on surfaces, the influence of the MWL on frost nucleation and propagation has not yet been previously addressed in the literature. To study the effect of the MWL on surface freezing events, a range of surface-functionalized glass substrates were prepared. In situ monitoring of freezing events with thermal imaging allowed studying the effect of surface chemistry and environmental relative humidity (RH) on the thickness and continuity of the MWL. We argue that the observed icing nucleation and propagation kinetics are directly related to the presence and continuity of the MWL, which can be manipulated by controlling the environmental humidity and surface chemistry.

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Kaumera are extracellular polymeric substances (EPS) extracted from excess aerobic granular sludge from Nereda® wastewater treatment plants. Kaumera exhibits significant market potential across diverse applications, fostering rapid research and business development. Furthermore, it will begin to be extracted from numerous installations worldwide. This calls for standard methods as analogue to (waste)water and sludge characterization. Due to lack of standardization, stakeholders are currently using different extraction and characterization protocols, impeding the development of a more uniform product and comparison of results across research studies. To address this, this report compiles the standard protocol for Kaumera extraction in the laboratory and for on-site and lab characterization to be used by researchers, the public Dutch water authorities, and the private industry. The procedures detailed in this document are in accordance with EPS research conducted at TU Delft and methodologies employed in Kaumera production facilities. This report aids in monitoring Kaumera characteristics worldwide and for optimizing the extraction process (including up and downstream processing). This will help maximize repeatability, interoperability, and quality and therefore accelerate business and research development, paving the way to develop a product that meets the needs of the endusers. Through the widespread adoption of this manual, our aim is to foster greater coordination and collaboration among stakeholders, thereby expediting the realization of Kaumera's full potential. @en

The use of the consistency index, as determined from fitting rheological data to the Herschel–Bulkley model, is described such that it may yield systematic trends that allow a very convenient description of the dissipative flow properties of linear and branched (bio)polymers in general, both in molecular and weakly associated supramolecular solutions. The effects of charge-mediated interactions by the systematic variation of the ionic strength and hydrogen bonding by a systematic variation in pH, using levels that are frequently encountered in systems used in practice, is investigated. These effects are then captured using the associated changes in the intrinsic viscosity to highlight the above-mentioned trends, while it also acts as an internal standard to describe the data in a concise form. The trends are successfully captured up to 100 times the polymer coil overlap and 100,000 times the solvent viscosity (or consistency index). These results therefore enable the rapid characterization of biopolymer systems of which the morphology remains unknown and may continue to remain unknown due to the wide-ranging monomer diversity and a lack of regularity in the structure, while the macromolecular coil size may be determined readily. @en

This study intends to develop design rules for binary mixture of gelators that govern their assembly behavior and subsequently explore the impact of their supramolecular assembly patterns on the gels’ rheological properties. To achieve these goals, nBA gelators with odd and even parities [n-methylene spacers between the amide groups (n = 5-10) and 17 carbons at each end] were blended at different ratios. Such bisamides with simple structures were selected to study because their different spacer lengths offer the possibility to have matching or non-matching hydrogen bonds. The results show that the assembly behavior of binary mixtures of bisamide gelators is the same in the solid and gel states. Binary mixtures of gelators, which only differ two methylene moieties in the spacer length, form compounds and co-assemble into fibers and sheets observed for (5BA)₁(7BA)₁ and (6BA)₁(8BA)₁ mixtures, respectively. Binary gelator mixtures of the same parity and a larger spacer length difference still lead to mixing for the odd parity couple (5BA)₁(9BA)₁₎, but to partial phase separation for the even parity mixture (6BA)₁(10BA)₁. Binary mixtures of gelators of different parities gave complete phase separation in the solid state, and self-sorted gels consisting of discrete fibers and sheets in the gels of (5BA)₃(6BA)₁ and (5BA)₃(10BA)₁. The even-even binary gels (20 wt %) consisting of co-assembled sheets show higher G′ than odd-odd binary gels (20 wt %) consisting of co-assembled fibers. In general, the self-sorting of odd and even molecules into the separate primary structures results in a dramatic decrease of G′ compared to the co-assembled gels (20 wt %), except for (5BA)₁(9BA)₁ gel (20 wt %). It might be due to larger woven spheres in (5BA)₁(9BA)₁ gel (20 wt %), which probably have a less entangled gel network.

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Ultrasound is widely used in medical imaging, and photo-acoustics is an upcoming imaging modality for the diagnosis of diseases. Future applications require a large matrix of small, sensitive, and broadband ultrasound sensors. However, current high-end systems still use piezo-electric material to detect ultrasound, with limited sensitivity and bandwidth. Silicon photonic circuits can meet the requirements of size, bandwidth, and scalability when designed as ultrasound sensors. Namely, a silicon photonic waveguide deforms when the ultrasound pressure waves impinge on it, leading to a change in effective refractive index, n_e, due to geometrical and photo-elastic effects [1]. However, these effects are weak, which limits the intrinsic sensitivity of silicon photonic ultrasound sensors [2]. To significantly enhance sensitivity, silicon waveguides have been combined with acousto-mechanical structures, which achieved acoustomechanical-noise-limited sensing [3], but this is not compatible with standard photonic platforms. Besides that, recent demonstrations of waveguides coated with polymers also improved sensitivity of the silicon photonic ultrasound sensors significantly, but not sufficient to reach acoustomechnical-noise-limited sensing [4]. Here, we study the effect of mechanical and opto-mechanical properties of polymer claddings on the sensitivity of silicon photonic ultrasound sensors. Our aim is to enhance the sensitivity of these devices by implementing tailored polymer coatings. First, we model the refractive index sensitivity of these type of waveguides, i.e. the change in effective refractive index n_e due to the incident ultrasound plane-wave with a pressure P, and we (Equation presented) where n_c, p₁₂, E, and v are refractive index, elasto-optic coefficient, Young's modulus (stiffness), and Poisson's ratio of the cladding material, respectively. We assume the change in cladding index dominates sensitivity.

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We present a sustainable, inherently safe battery chemistry that is based on widely available and cheap materials, that is, iron and manganese hosted in alginate bio-material known from the food and medical industry. The resulting battery can be recycled to allow circularity. The electrodes were synthesised by the alginate caging the multi-valent metals to form a hydrogel in an aqueous environment. Characterisation includes FTIR, XPS and Mössbauer spectroscopy. The electrochemical performance of the electrodes was investigated by performing cyclic voltammetry (CV) and (dis)charge experiments. Mn and Fe ions show good co-ordination with the alginic acid with higher oxidation states demonstrating complex bonding behaviour. The non-optimised iron and manganese alginate electrodes already exhibit a cycling efficiency of 98% and 69%, respectively. This work shows that Fe and Mn atomically disperse in a bio-based host material and can act as electrodes in an aqueous battery chemistry. While demonstrated at cell level, it is furthermore explained how these materials can form the basis for a (semi-solid) flow cell.

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Biopolymers are abundant, renewable, and biodegradable resources. However, bio-based materials often require toughening additives, like (co)polymers or small plasticizing molecules. Plasticization is monitored via the glass transition temperature versus diluent content. To describe this, several thermodynamic models exist; nevertheless, most expressions are phenomenological and lead to over-parametrization. They also fail to describe the influence of sample history and the degree of miscibility via structure-property relationships. We propose a new model to deal with semi-compatible systems: the generalized mean model, which can classify diluent segregation or partitioning. When the constant k_GM is below unity, the addition of plasticizers has hardly any effect, and in some cases, even anti-plasticization is observed. On the other hand, when the k_GM is above unity, the system is highly plasticized even for a small addition of the plasticizer compound, which indicates that the plasticizer locally has a higher concentration. To showcase the model, we studied Na-alginate films with increasing sizes of sugar alcohols. Our k_GM analysis showed that blends have properties that depend on specific polymer interactions and morphological size effects. Finally, we also modeled other plasticized (bio)polymer systems from the literature, concluding that they all tend to have a heterogeneous nature.

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Tailoring the order in hierarchical structures is a key goal of bioinspired nanocomposite design. Recently, nacre-like materials have been developed by solvent evaporation methods that are scalable and attain advanced functionalities. However, understanding the alignment mechanisms of 2D fillers, nanosheets, or platelets remains challenging. This work explores possible pathways for nanocomposite ordering via orientation distribution functions. We demonstrate how the immobilization of 2D materials via (pseudo)network formation is crucial to alignment based on evaporation. We show a modified affine deformation model that describes such evaporative methods. In this, a gel network develops enough yield stress and uniformly deforms as drying proceeds, along with the immobilized particles, causing an in-plane orientation. Herein, we tested the dominance of this approach by using a thermo-reversible gel for rapid montmorillonite (MMT) particle fixation. We researched gelatin/MMT as a model system to investigate the effects of high loadings, orientational order, and aspect ratio. The nacre-like nanocomposites showed a semiconstant order parameter (⟨P₂⟩ ∼ 0.7) over increasing nanofiller content up to 64 vol % filler. This remarkable alignment resulted in continuously improved mechanical and water vapor barrier properties over unusually large filler fractions. Some variations in stiffness and diffusion properties were observed, possibly correlated to the applied drying conditions of the hybrid hydrogels. The affine deformation strategy holds promise for developing next-generation advanced materials with tailored properties even at (very) high filler loadings. Furthermore, a gelling approach offers the advantages of simplicity and versatility in the formulation of the components, which is useful for large-scale fabrication methods.

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We report a systematic study of the gelation behavior of nBA gelators in xylene, with odd and even n-methylene spacers between the amide groups (n = 5-10) and 17 carbons at each end. The melting temperatures (Tm0) of nBA gels are obtained from fitting our DSCN(T) model to the experimental DSC data. The found Tm0 of nBA gels is about 35 °C lower than Tm0 of the pure nBA gelators. This is reasonably well explained by a simple model combining theories of Flory-Huggins and Gibbs free energy of melting (FHM model). We attribute this depression to an increase in entropy upon melting of the gel due to mixing with the solvent. The odd-even alternation in Tm0 of nBA gels, which was also found for the nBA gelators, indicates that the solid structures inside the gels are somewhat similar. This was studied using XRD: similar 00l reflections were found in the XRD patterns of all nBA gels and their nBA gelators. For even nBA gels, the same reflections in the 19-25° (2θ) region confirm that the sheetlike supramolecular structure of the gels is analogous to the lamellar structure of the solid gelators. For odd nBA gels, a slight difference in the reflections around 20-25° (2θ) implies a somewhat different side-by-side packing of odd nBA gels compared to the solid state. This variation is found for all the odd gels, and indeed, they show distinctly different morphologies compared to the even nBA gels. The possible effect of this on the rheological properties is discussed using some inspiration from the Halpin-Tsai model for composites where nBA gels are considered to be analogous to composite materials. The change of the storage modulus (G') with the shape factor of woven fibers and sheets in nBA gels (20 wt %) indicates that a rheological odd-even effect might indeed be present.

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High-performance bioinspired materials have shown rapid development over the last decade. Examples are brick-and-mortar hierarchical structures, which are often achieved via solvent evaporation. Although good properties are claimed, most systems are composed of stacked or intercalated platelets. Exfoliation is a crucial step to give ultimate anisotropic properties, e.g., thermal, mechanical, and barrier properties. We propose a general framework for all the various types of micro-scale structures that should be distinguished for 2D filler nanocomposites. In particular, the exfoliated state is systematically explored by the immobilization of montmorillonite platelets via (gelatin) hydrogelation. Scattering techniques were used to evaluate this strategy at the level of the particle dispersion and the regularity of spatial arrangement. The gelatin/montmorillonite exfoliated nanostructures are fully controlled by the filler volume fraction since the observed gallery d-spacings perfectly fall onto the predicted values. Surprisingly, X-ray analysis also revealed short- and quasi long-range arrangement of the montmorillonite clay at high loading.

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We have developed an analytical method to quantitatively analyze differential scanning calorimetry (DSC) experimental data. This method provides accurate determination of thermal properties such as equilibrium melting temperature, latent heat, change of heat capacity which can be performed automatically without intervention of a DSC operator. DSC is one of the best techniques to determine the thermal properties of materials. However, the accuracy of the transition temperature and enthalpy change can be affected by artifacts caused by the instrumentation, sampling, and the DSC analysis methods which are based on graphical constructions. In the present study, an analytical function (DSC_N(T)) has been developed based on an assumed Arrhenius crystal size distribution together with instrumental and sample-related peak broadening. The DSC_N(T) function was successfully applied to fit the experimental data of a substantial number of calibration and new unknown samples, including samples with an obvious asymmetry of the melting peak, yielding the thermal characteristics such as melting and glass transition temperature, and enthalpy and heat capacity change. It also allows very accurate analysis of binary systems with two distinct but severely overlapping peaks and samples that include a cold crystallization before melting.

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The interaction between a turbulent boundary layer flow and compliant surfaces is investigated experimentally. Three viscoelastic coatings with different material stiffnesses are used to identify the general surface response to the turbulent flow conditions. For the softest coating, the global force measurements show two obvious regimes of interaction with an indicated transition at Ub/Ct∼3.5, where Ub is the bulk flow velocity and Ct is the coating shear velocity. The one-way coupled regime shows friction values comparable to those of the rigid wall, while the two-way coupled regime indicate a significant increase in fluid friction. Within the one-way coupled regime for Ub/Ct>1.2, the flow measurements show a low level of two-way coupling represented by the change of the velocity profile as well as the increase in the Reynolds stresses in the near-wall region. This is supported by the surface deformation measurements. Initially, the turbulent flow structures induce only an imprint on the coating surface, while a change in surface response occurs when the surface wave propagation velocity cw equals the shear wave velocity of the coating Ct (i.e. cw/Ct∼1). Above Ub/Ct>1.2, a growth in wavelength is observed with increasing flow velocity, most probably due to the surface wave formation generated downstream the pressure features of the flow. The surface response is stable and correlates with the high-intensity turbulent pressure fluctuations in the turbulent boundary layer, with a wave propagation velocity cw∼0.7–0.8Ub. Within the two-way coupled regime, additional fluid motions and a downward shift in the logarithmic region of the velocity profile are observed due to substantial surface deformation and confirm the frictional drag increase. Another type of surface response is initiated by phase-lag instability in combination with surface undulations that start to protrude the viscous sublayer, where the propagation velocity of surface wave trains is cw∼0.17–0.18Ub.@en

(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) obtained from waste/wastewater using a mixed microbial culture (MMC) usually varies in its properties due to daily variation in the waste/wastewater composition applied as feedstock. In the current study, the average molecular weight (MW) of PHBV was purposely reduced from about 1 MDa to about 200 kDa by drying the PHBV-rich biomass at elevated temperature of 120 °C for 18 h to ease extraction and handling. Furthermore, conversion into value-added chemicals such as trans-crotonic acid (trans-CA) and trans-2-pentenoic acid (2-PA) by thermal decomposition (pyrolysis) benefits from the lower MW. For the extraction of low MW PHBV, the use of the bio-based solvents 2-methyltetrahydroxyfuran (2-MTHF) and dihydrolevoglucosenone (cyrene) was studied. The maximum extraction yield of 62 ± 3 % with purity of > 99 % was achieved with 2-MTHF at 80 °C for an hour with high biomass to solvent ratio of 5 % (g/mL). Cyrene-based extractions resulted in the highest yield of 57 ± 2 % with purity of > 99 % at 120 °C in 2 h with 5 % (g/mL) biomass to solvent ratio. The mass balance closure over the extraction process indicated that about 15 % and 10 % of polymer has remained in the residual biomass after extraction by 2-MTHF and cyrene, respectively. The performance of these new solvents to extract polymers with various average MW was compared to the benchmark extractions using chloroform and dimethyl carbonate (DMC). It was found that for the polymers with low average MW the extraction efficiency of the proposed solvents exceeds the benchmark solvents.

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We report on the morphology and mechanical properties of nanocomposite films derived from aqueous, hybrid liquid crystalline mixtures of rodlike aggregates of a sulfonated, all-aromatic polyamide, poly(2,2′-disulfonyl-4,4′-benzidine terephthalamide) (PBDT), and graphene oxide (GO) platelets. An isothermal step at 200 °C facilitates in situ partial thermal reduction of GO to reduced GO (rGO) in nanocomposite films. X-ray scattering studies reveal that PBDT-rGO nanocomposites exhibit both higher in-plane alignment of PBDT (the order parameter increases from 0.79 to 0.9 at 1.8 vol % rGO) and alignment along the casting direction (from 0.1 to 0.6 at 1.8 vol % rGO). From dynamic mechanical thermal analysis, the interaction between PBDT and rGO causes the β-relaxation activation energy for PBDT to increase with rGO concentration. Modulus mapping of nanocomposites using atomic force microscopy demonstrates enhanced local stiffness, indicating reinforcement. From stress-strain analysis, the average Young's modulus increases from 16 to 37 GPa at 1.8 vol % rGO and the average tensile strength increases from 210 to 640 MPa. Despite polymer alignment along the casting direction, an average transverse tensile strength of 230 MPa is obtained.

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The biotechnological production of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) derived from organic waste streams by mixed microbial communities is well established at the pilot-level. However, there is limited research on the recovery of the biopolymer from the microbial biomass, while its impact on product quality and product costs is major. When applying solvent extraction, the choice of solvent has a profound influence on many aspects of the process design. This study provides a framework to perform a systematic solvent screening for PHBV extraction. First, a database was constructed of 35 solvents that were assessed according to six different selection criteria. Then, six solvents were chosen for further experimental analysis, including 1-butanol, 2-butanol, 2-ethyl hexanol (2-EH), dimethyl carbonate (DMC), methyl isobutyl ketone (MIBK), and acetone. The main findings are that the extractions with acetone and DMC obtained the highest yields (91-95%) with reasonably high purities (93-96%), where acetone had a key advantage of the possibility to use water as anti-solvent. Moreover, the results provided new insights in the mechanisms behind PHBV extraction by pointing out that at elevated temperatures the extraction efficiency is less determined by the solvent's solubility parameters and more determined by the solvent size. Although case-specific factors play a role in the final solvent choice, we believe that this study provides a general strategy for the solvent selection process.

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The crystal structure and phase behavior of bisamide gelators are investigated using differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy, X-ray diffraction (XRD), and molecular modeling, aiming at a better understanding of bisamide gel systems. A homologous series of bisamide model compounds (nBAs) was prepared with the (CH₂)_nspacer between the two amide groups, where n varies from 5 to 10, and with two symmetric C17 alkyl tails. With increasing spacer length, the thermal properties show a clear odd-even effect, which was characterized using our newly developed analytical model DSC_N(T). Using XRD, all studied nBA compounds turn out to have a layer-like structure. The XRD patterns of the odd BA series are very similar but show marked differences compared to the XRD patterns of the even series, which in turn are very similar. The odd-membered 5BA molecules are nearly perpendicular to the stacked layers, as described by a pseudo-orthorhombic unit cell, whereas the even-membered 6BA molecules are tilted at an angle with respect to the layer normal, as described by a triclinic unit cell. In both the odd and even series, the inter-layer interaction is the van der Waals interaction. The 6BA hydrogen bonding scheme is very similar to that of Nylon 6,10 α, unlike the 5BA H bonding scheme. The packing of the C17 alkyl tails in the 5BA layers is similar to polyethylene, and unlike 6BA. The slightly higher crystalline density of 6BA (1.038 g cm^-3) as compared to 5BA (1.018 g cm^-3) explains the higher melting point, higher enthalpy of fusion, and the observed shift of N-H stretch bands to higher wave numbers. The structural differences observed between the odd and even BA series reflect the different structure-directing effect of parallel versus antiparallel amide hydrogen bonding motifs. These differences underlie the observed odd-even effect in the thermal properties of nBA compounds.

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