Hossein Najaf Zadeh

This study investigates the 3D extrusion printing of a carboxymethyl cellulose (CMC)–gelatin complex coacervate system. Various CMC–gelatin coacervate hydrogels were prepared and analyzed to achieve this goal. The impact of the CMC–gelatin ratio, pH, and total biopolymer concentration on coacervation formation and rheological properties was evaluated to characterize the printability of the samples. Turbidity results indicated that the molecular interactions between gelatin and CMC biopolymers are significantly pH-dependent, occurring within the range of pH 3.7 to pH 5.6 for the tested compositions. Confocal Laser Scanning Microscopy (CLSM) confirmed the presence of coacervates as spherical particles within the optimal coacervation range. Scanning electron microscopy micrographs supported the CLSM findings, revealing greater porosity within this optimal pH range. Rheological characterization demonstrated that all CMC–gelatin hydrogels exhibited pseudoplastic behavior, with an inverse correlation between increased coacervation and decreased shear viscosity. Additionally, the coacervates displayed lower tackiness compared to gelatin hydrogels, with the maximum tackiness normal force for various CMC–gelatin ratios ranging from 1 to 15 N, notably lower than the 29 N observed for gelatin hydrogels. Mixtures with CMC–gelatin ratios of 1:15 and 1:20 exhibited the best shear recovery behavior, maintaining higher strength after shear load. The maximum strength of the CMC–gelatin coacervate system was found at a biopolymer concentration of 6%. However, lower biopolymer content allowed for consistent extrusion. Importantly, all tested samples were successfully extruded at 22 ± 2 °C, with the 1:15 biopolymer ratio yielding the most consistent printed quality. Our research highlights the promise of the CMC–gelatin coacervate system for 3D printing applications, particularly in areas that demand precise material deposition and adjustable properties.

Amidst population growth and challenges with existing fertilizers, the development of smart and environmentally friendly agrochemicals is imperative. While 3D printing is widespread, its potential in slow-release agrochemicals remains unexplored. This proof-of-concept study employed solvent casting and 3D printing to develop agar–urea structures. These structures, comprising 2.5% (w/w) agar, incorporated either 7% (w/w) or 13% (w/w) urea as nitrogen nutrients. Rheological, mechanical, and morphological properties and sorption capabilities were explored. Rheological analysis revealed a substantial impact of urea, enhancing material resistance to deformation. In mechanical tests, inclusion of urea showed no significant impact on compressive strength. SEM analysis confirmed the successful entrapment of urea within the agar matrix. The inclusion of urea resulted in a diminished water sorption capacity, attributed to the urea–water interactions disrupting the hydrogen bonding ability of agar. Agar–urea inks were employed in 3D printing utilizing the direct-ink writing technique, and the nitrogen release behavior was investigated. Results revealed nearly complete urea release in the positive control within 48 h. In contrast, agar–urea formulations with 7% (w/w) and 13% (w/w) achieved nitrogen release rates of 88.8% and 94.4%, respectively, suggesting potential for 3D-printed agar formulations to modify the immediate release behavior seen in conventional urea fertilizers.

Screen-additive manufacturing (SAM) is a potential method for producing small intricate parts without waste generation, offering minimal production cost. A wide range of materials, including gels, can be shaped using this method. A gel material is composed of a three-dimensional cross-linked polymer or colloidal network immersed in a fluid, known as hydrogel when its main constituent fluid is water. Hydrogels are capable of absorbing and retaining large amounts of water. Cellulose gel is among the materials that can form hydrogels and, as shown in this work, has the required properties to be directly SAM, including shear thinning and formation of post-shearing gel structure. In this study, we present the developed method of SAM for the fabrication of complex-shaped cellulose gel and examine whether successive printing layers can be completed without delamination. In addition, we evaluated cellulose SAM without the need for support material. Design of Experiments (DoE) was applied to optimize the SAM settings for printing the novel cellulose-based gel structure. The optimum print settings were then used to print a periodic structure with micro features and without the need for support material.

To facilitate functional hydrogel part production using the indirect wax mould method, it is necessary to understand the relationships between materials, process and mould removal. This research investigated the thermophysical properties, wettability and surface roughness of wax template moulds in the production of cellulose hydrogel objects. Cellulose gel was thermally formed and shaped in three different wax moulds—high melting point paraffin, sacrificial investment casting wax and Solidscape^® wax—by physical cross-linking of polymer networks of cellulose solution in NaOH/urea aqueous solvent. All three wax moulds were capable of casting cellulose hydrogel objects. Cellulose gelling time was reduced by increasing the temperature. Thus, the mould melting temperature had a direct effect on the gelling time. It was found that mould removal time varied based on the contact angle (CA) of the cellulose solution and the mould, and based on the melting point of the mould. A higher CA of cellulose solution on the wax moulds resulted in faster mould removal. When melting the wax in 90 °C water, high melting point paraffin, sacrificial investment casting and Solidscape^® wax took about 3, 2 and 1.5 h, respectively, to remove the moulds from the cellulose gel.

In recent years, 3D printing has enabled the fabrication of complex designs, with low-cost customization and an ever-increasing range of materials. Yet, these abilities have also created an enormous challenge in optimizing a large number of process parameters, especially in the 3D printing of swellable, non-toxic, biocompatible and biodegradable materials, so-called bio-ink materials. In this work, a cellulose gel, made out of aqueous solutions of cellulose, sodium hydroxide and urea, was used to demonstrate the formation of a shear thinning bio-ink material necessary for an extrusion-based 3D printing. After analysing the shear thinning behaviour of the cellulose gel by rheometry a Design of Experiments (DoE) was applied to optimize the 3D bioprinter settings for printing the cellulose gel. The optimum print settings were then used to print a human ear shape, without a need for support material. The results clearly indicate that the found settings allow the printing of more complex parts with high-fidelity. This confirms the capability of the applied method to 3D print a newly developed bio-ink material.