Instytut Podstawowych Problemów Techniki

Lisowski P., Jóźwiak-Niedźwiedzka D., Osial M., Bochenek K., Denis P., Glinicki M. A., Power ultrasound-assisted enhancement of granulated blast furnace slag reactivity in cement paste, CEMENT AND CONCRETE COMPOSITES, ISSN: 0958-9465, DOI: 10.1016/j.cemconcomp.2024.105781, Vol.154, No.105781, pp.1-19, 2024

Abstract:
This paper introduces a first-time investigation into the impact of power ultrasound (PUS)-assisted preparation on the physicochemical and mechanical properties of cement-granulated blast furnace slag (GBFS) composite pastes. Pastes containing deposited GFBS with varying particle size fractions, partially replacing Portland cement, were prepared using PUS (ultrasonic horn tip, 20 kHz, 700 W) in pulse mode in a vertical jacketed glass sonoreactor with closed-circuit cooling. Cement paste incorporating 20 wt.% GBFS as mass substitution with varying particle size fractions was characterized by several physicochemical techniques at different curing ages. Exploring the cement and GBFS interaction induced by PUS, the compressive and flexural strength, the elastic modulus and indentation hardness, the heat of hardening, the mineral composition of hydration products, and the specific surface area BET were evaluated for a curing time of up to 28 days. The grain size distribution of GFBS and the reaction mixture's pH were measured. Both mechanical properties, heat of hydration and nanoporosity exhibited strong sensitivity to PUS treatment. Sonofragmentation of GBFS particles (especially the 125–250 μm fraction) increased with increasing sonication time, resulting in a relative increase of fraction <63 μm and a decrease of fraction >125 μm by 275 % and 60 %, respectively. Using the obtained SEM-EDS data, a simplified mechanism is proposed to explain the effects induced by PUS treatment.

Keywords:
Power ultrasound treatment, Portland cement, Granulated blast furnace slag, Early strength development, C-S-H/C-A-S-H, Seeding effect

Zaszczyńska A., Gradys A.D., Ziemiecka A., Szewczyk P., Tymkiewicz R., Lewandowska-Szumieł M., Stachewicz U., Sajkiewicz P.Ł., Enhanced Electroactive Phases of Poly(vinylidene Fluoride) Fibers for Tissue Engineering Applications, International Journal of Molecular Sciences, ISSN: 1422-0067, DOI: 10.3390/ijms25094980, Vol.25, No.9, pp.4980-1-25, 2024

Abstract:
Nanofibrous materials generated through electrospinning have gained significant attention in tissue regeneration, particularly in the domain of bone reconstruction. There is high interest in designing a material resembling bone tissue, and many scientists are trying to create materials applicable to bone tissue engineering with piezoelectricity similar to bone. One of the prospective candidates is highly piezoelectric poly(vinylidene fluoride) (PVDF), which was used for fibrous scaffold formation by electrospinning. In this study, we focused on the effect of PVDF molecular weight (180,000 g/mol and 530,000 g/mol) and process parameters, such as the rotational speed of the collector, applied voltage, and solution flow rate on the properties of the final scaffold. Fourier Transform Infrared Spectroscopy allows for determining the effect of molecular weight and processing parameters on the content of the electroactive phases. It can be concluded that the higher molecular weight of the PVDF and higher collector rotational speed increase nanofibers’ diameter, electroactive phase content, and piezoelectric coefficient. Various electrospinning parameters showed changes in electroactive phase content with the maximum at the applied voltage of 22 kV and flow rate of 0.8 mL/h. Moreover, the cytocompatibility of the scaffolds was confirmed in the culture of human adipose-derived stromal cells with known potential for osteogenic differentiation. Based on the results obtained, it can be concluded that PVDF scaffolds may be taken into account as a tool in bone tissue engineering and are worth further investigation.

Keywords:
scaffolds,polymers,piezoelectricity,bone tissue engineering,nanofibers,regenerative medicine

Nwaji N., Fikadu B., Osial M., Moazzami Goudarzi Z., Asgaran S., Teshome Tufa L., Lee J., Giersig M., Disentangling the catalytic origin in defect engineered 2D NiCoMoS@Ni(CN)2 core-shell heterostructure for energy-saving hydrazine-assisted water oxidation, International Journal of Hydrogen Energy, ISSN: 0360-3199, DOI: 10.1016/j.ijhydene.2024.08.432, Vol.86, pp.554-563, 2024

Abstract:
The major hindrance to efficient electrocatalytic hydrogen generation from water electrolysis is the sluggish kinetics with corresponding large overvoltage of oxygen evolution reaction. Herein, we report a defective 2D NiCoMoS@Ni(CN)2 core-shell heterostructure derived from Hofmann-type MOF as an efficient and durable high-performance noble metal-free electrocatalyst for hydrazine oxidation reaction (HzOR) in alkaline media. The sluggish oxygen evolution reaction was replaced with a more thermodynamically favourable HzOR, enabling energy-saving electrochemical hydrogen production with 2D NiCoMoS@Ni(CN)2 acting as a bifunctional electrocatalyst for anodic HzOR and cathodic hydrogen generation. Operating at room temperature, the two-electrode electrolyzer delivers 100 mA cm−2 from a cell voltage of just 257 mV, with strong long-term electrochemical durability and nearly 100% Faradaic efficiency for hydrogen evolution in 1.0 M KOH aqueous solution with 0.5 M hydrazine. The density functional theory (DFT) was employed to investigate the origin of catalytic performance and showed that high vacancy creation within the heterointerface endowed NiCoMoS@Ni(CN)2 with favourable functionalities for excellent catalytic performance.

Keywords:
Defect engineering, Core-shell, Electrocatalyst, Hydrazine oxidation, Heterostructure

Moazzami Goudarzi Z., Zaszczyńska A., Kowalczyk T., Sajkiewicz P.Ł., Electrospun Antimicrobial Drug Delivery Systems and Hydrogels Used for Wound Dressings, Pharmaceutics, ISSN: 1999-4923, DOI: 10.3390/pharmaceutics16010093, Vol.16, No.1, pp.93-1-27, 2024

Abstract:
Wounds and chronic wounds can be caused by bacterial infections and lead to discomfort in patients. To solve this problem, scientists are working to create modern wound dressings with antibacterial additives, mainly because traditional materials cannot meet the general requirements for complex wounds and cannot promote wound healing. This demand is met by material engineering, through which we can create electrospun wound dressings. Electrospun wound dressings, as well as those based on hydrogels with incorporated antibacterial compounds, can meet these requirements. This manuscript reviews recent materials used as wound dressings, discussing their formation, application, and functionalization. The focus is on presenting dressings based on electrospun materials and hydrogels. In contrast, recent advancements in wound care have highlighted the potential of thermoresponsive hydrogels as dynamic and antibacterial wound dressings. These hydrogels contain adaptable polymers that offer targeted drug delivery and show promise in managing various wound types while addressing bacterial infections. In this way, the article is intended to serve as a compendium of knowledge for researchers, medical practitioners, and biomaterials engineers, providing up-to-date information on the state of the art, possibilities of innovative solutions, and potential challenges in the area of materials used in dressings.

Keywords:
wound dressings, drug delivery systems, thermoresponsive hydrogels

Haghighat Bayan M.A., Rinoldi C., Rybak D., Zargarian S.S., Zakrzewska A., Miler O., Põhako-Palu K., Zhang S., Stobnicka-Kupiec A., Górny Rafał L., Nakielski P., Kogermann K., De Sio L., Ding B., Pierini F., Engineering surgical face masks with photothermal and photodynamic plasmonic nanostructures for enhancing filtration and on-demand pathogen eradication, Biomaterials Science, ISSN: 2047-4849, DOI: 10.1039/d3bm01125a, Vol.12, No.4, pp.949-963, 2024

Abstract:
The shortage of face masks and the lack of antipathogenic functions has been significant since the recent pandemic's inception. Moreover, the disposal of an enormous number of contaminated face masks not only carries a significant environmental impact but also escalates the risk of cross-contamination. This study proposes a strategy to upgrade available surgical masks into antibacterial masks with enhanced particle and bacterial filtration. Plasmonic nanoparticles can provide photodynamic and photothermal functionalities for surgical masks. For this purpose, gold nanorods act as on-demand agents to eliminate pathogens on the surface of the masks upon near-infrared light irradiation. Additionally, the modified masks are furnished with polymer electrospun nanofibrous layers. These electrospun layers can enhance the particle and bacterial filtration efficiency, not at the cost of the pressure drop of the mask. Consequently, fabricating these prototype masks could be a practical approach to upgrading the available masks to alleviate the environmental toll of disposable face masks.

Psiuk R., Chrzanowska-Giżyńska J., Denis P., Wyszkowska E., Wiśniewska M., Lipińska M., Wojtiuk E., Kurpaska Ł., Smolik J., Mościcki T. P., Microstructural and properties investigations of tantalum-doped tungsten diboride ceramic coatings via HiPIMS and RF magnetron sputtering, ARCHIVES OF CIVIL AND MECHANICAL ENGINEERING, ISSN: 1644-9665, DOI: 10.1007/s43452-024-01050-0, Vol.24, No.239, pp.1-16, 2024

Abstract:
In this work, tantalum-doped tungsten boride ceramic coatings were deposited from a single sputtering target with the radio frequency (RF) and high-power impulse magnetron sputtering (HiPIMS) methods. Two-inch torus targets were synthesised from pure elements with the spark plasma sintering (SPS) method with a stoichiometric composition of W1-xTaxB2.5 (x = 0, 0.08, 0.16, 0.24). Films were deposited with RF and HiPIMS power suppliers at process temperatures from RT to 600 °C. The substrate heating and the energy of the ionised material impacting the substrate increase the surface diffusivity of adatoms and are crucial in the deposition process. The results of SEM and XRD investigations clearly show that the addition of tantalum also changes the microstructure of the deposited films. The coatings without tantalum possess a finer microstructure than those with 24% of tantalum. The structure of films is homogeneous along the film thickness and composed mainly of columns with a (0001) preferred orientation. Deposited coatings are composed mainly of P6/mmm α-WB2 structures. The analysis of nanoindentation results allowed us to determine that ceramic coatings obtained with the HiPIMS method possess hardness above 41 GPa and a ratio of hardness to reduced Young modulus above 0.1. The thickness of HiPIMS-deposited films is relatively small: only around 60% of the RF magnetron sputtered coatings even when the average power input was two times higher. However, it has been shown that the RF coatings require heating the substrate above 400 °C to obtain a crystalline structure, while the HiPIMS method allows for a reduction of the substrate temperature to 300 °C.

Keywords:
RF magnetron sputtering, HiPIMS magnetron sputtering, Superhard ceramic coatings, Transition metal borides, Deposition temperature

Bandzerewicz A., Howis J., Wierzchowski K., Miroslav S., Jiri H., Denis P., Gołofit T., Pilarek M., Gadomska-Gajadhur A., Exploring the application of poly(1,2-ethanediol citrate)/polylactide nonwovens in cell culturing, Frontiers in Bioengineering and Biotechnology, ISSN: 2296-4185, DOI: 10.3389/fbioe.2024.1332290, Vol.12, pp.1-13, 2024

Abstract:
Biomaterials containing citric acid as a building unit show potential for use as blood vessel and skin tissue substitutes. The success in commercializing implants containing a polymer matrix of poly(1,8-octanediol citrate) provides a rationale for exploring polycitrates based on other diols. Changing the aliphatic chain length of the diol allows functional design strategies to control the implant’s mechanical properties, degradation profile and surface energy. In the present work, poly(1,2-ethanediol citrate) was synthesized and used as an additive to polylactide in the electrospinning process. It was established that the content of polycitrate greatly influences the nonwovens’ properties: an equal mass ratio of polymers resulted in the best morphology. The obtained nonwovens were characterized by surface hydrophilicity, tensile strength, and thermal properties. L929 cell cultures were carried out on their surface. The materials were found to be non-cytotoxic and the degree of porosity was suitable for cell colonization. On the basis of the most important parameters for assessing the condition of cultured cells (cell density and viability, cell metabolic activity and lactate dehydrogenase activity), the potential of PLLA + PECit nonwovens for application in tissue engineering was established.

Zaszczyńska A., Kołbuk-Konieczny D., Gradys A. D., Sajkiewicz P. Ł., Development of Poly(methyl methacrylate)/nano-hydroxyapatite (PMMA/nHA) Nanofibers for Tissue Engineering Regeneration Using an Electrospinning Technique, Polymers, ISSN: 2073-4360, DOI: 10.3390/polym16040531, Vol.16, No.4, pp.531-1-19, 2024

Abstract:
The study explores the in vitro biocompatibility and osteoconductivity of poly(methyl methacrylate)/nano-hydroxyapatite (PMMA/nHA) composite nanofibrous scaffolds for bone tissue engineering (BTE). Electrospun scaffolds, exhibiting both low and high fiber orientation, were investigated. The inclusion of hydroxyapatite nanoparticles enhances the osteoconductivity of the scaffolds while maintaining the ease of fabrication through electrospinning. SEM analysis confirms the high-quality morphology of the scaffolds, with successful incorporation of nHA evidenced by SEM-EDS and FTIR methods. DSC analysis indicates that nHA addition increases the PMMA glass transition temperature (Tg) and reduces stress relaxation during electrospinning. Furthermore, higher fiber orientation affects PMMA Tg and stress relaxation differently. Biological studies demonstrate the composite material’s non-toxicity, excellent osteoblast viability, attachment, spreading, and proliferation. Overall, PMMA/nHA composite scaffolds show promise for BTE applications.

Keywords:
biomaterials, nanofibrous scaffolds, bone tissue engineering

Staszczak M., Urbański L., Gradys A. D., Cristea M., Pieczyska E. A., Nucleation, Development and Healing of Micro-Cracks in Shape Memory Polyurethane Subjected to Subsequent Tension Cycles, Polymers, ISSN: 2073-4360, DOI: 10.3390/polym16131930, Vol.16, No.13, pp.1-22, 2024

Abstract:
Thermoresponsive shape memory polymers (SMPs) have garnered increasing interest for their exceptional ability to retain a temporary shape and recover the original configuration through temperature changes, making them promising in various applications. The SMP shape change and recovery that happen due to a combination of mechanical loading and appropriate temperatures are related to its particular microstructure. The deformation process leads to the formation and growth of micro-cracks in the SMP structure, whereas the subsequent heating over its glass transition temperature Tg leads to the recovery of its original shape and properties. These processes also affect the SMP microstructure. In addition to the observed macroscopic shape recovery, the healing of micro-crazes and micro-cracks that have nucleated and developed during the loading occurs. Therefore, our study delves into the microscopic aspect, specifically addressing the healing of micro-cracks in the cyclic loading process. The proposed research concerns a thermoplastic polyurethane shape memory polymer (PU-SMP) MM4520 with a Tg of 45 °C. The objective of the study is to investigate the effect of the number of tensile loading-unloading cycles and thermal shape recovery on the evolution of the PU-SMP microstructure. To this end, comprehensive research starting from structural characterization of the initial state and at various stages of the PU-SMP mechanical loading was conducted. Dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), wide-angle X-ray scattering (WAXS) and scanning electron microscopy (SEM) were used. Moreover, the shape memory behavior in the thermomechanical loading program was investigated. The obtained average shape fixity value was 99%, while the shape recovery was 92%, which confirmed good shape memory properties of the PU-SMP. Our findings reveal that even during a single loading-unloading tension cycle, crazes and cracks nucleate on the surface of the PU-SMP specimen, whereas the subsequent temperature-induced shape recovery process carried out at the temperature above Tg enables the healing of micro-cracks. Interestingly, the surface of the specimen after three and five loading-unloading cycles did not exhibit crazes and cracks, although some traces of cracks were visible. The traces disappeared after exposing the material to heating at Tg + 20 °C (65 °C) for 30 min. The crack closure phenomenon during deformation, even without heating over Tg, occurred within three and five subsequent cycles of loading-unloading. Notably, in the case of eight loading-unloading cycles, cracks appeared on the surface of the PU-SMP and were healed only after thermal recovery at the particular temperature over Tg. Upon reaching a critical number of cycles, the proper amount of energy required for crack propagation was attained, resulting in wide-open cracks on the material’s surface. It is worth noting that WAXS analysis did not indicate strong signs of typical highly ordered structures in the PU-SMP specimens in their initial state and after the loading history; however, some orientation after the cyclic deformation was observed.

Keywords:
polyurethane shape memory polymer, glass transition temperature, tensile loading cycles, structure analysis, micro-cracks, healing

Osial M., Wilczewski S., Godlewska U., Skórczewska K., Hilus J., Szulc J., Roszkiewicz-Walczuk A., Dąbrowska A., Moazzami Goudarzi Z., Lewandowski K., Wypych T., Nguyen Phuong T., Sumara G., Giersig M., Incorporation of Nanostructural Hydroxyapatite and Curcumin Extract from Curcuma longa L. Rhizome into Polylactide to Obtain Green Composite, Polymers, ISSN: 2073-4360, DOI: 10.3390/polym16152169, Vol.16, No.15, pp.2169-1-20, 2024

Abstract:
This study showed that a polylactide (PLA)-based composite filled with nanostructured hydroxyapatite (HAp) and a natural extract from the rhizome of Curcuma longa L. could provide an alternative to commonly used fossil-based plasticsfor food packaging. The incorporation of HAp into the PLA matrix had a positive effect on improving selected properties of the composites; the beneficial effect could be enhanced by introducing a green modifier in the form of an extract. Prior to the fabrication of the composite, the filler was characterized in terms of morphology and composition, and the composite was then fully characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), Raman and Fourier transform infrared spectroscopy (FT-IR), and the mechanical, thermal, thermomechanical, and optical properties were investigated. The proposed material exhibits antioxidant properties against DPPH radicals and antibacterial performance against Escherichia coli (E. coli). The results showed that the nanocomposite has the highest antioxidant and antibacterial properties for 10 wt% HAp with an average diameter of rod-shaped structures below 100 nm. In addition, the introduction of turmeric extract had a positive effect on the tensile strength of the nanocomposites containing 1 and 5% HAp. As the resulting material adsorbs light in a specific wavelength range, it can be used in the medical sector, food-packaging, or coatings.

Keywords:
polylactide, hydroxyapatite, turmeric extract, curcumin extract, green composite

Zaszczyńska A., Zabielski K., Gradys A. D., Kowalczyk T., Sajkiewicz P. Ł., Piezoelectric Scaffolds as Smart Materials for Bone Tissue Engineering, Polymers, ISSN: 2073-4360, DOI: 10.3390/polym16192797, Vol.16, No.19, pp.2797-1-30, 2024

Abstract:
Bone repair and regeneration require physiological cues, including mechanical, electrical, and biochemical activity. Many biomaterials have been investigated as bioactive scaffolds with excellent electrical properties. Amongst biomaterials, piezoelectric materials (PMs) are gaining attention in biomedicine, power harvesting, biomedical devices, and structural health monitoring. PMs have unique properties, such as the ability to affect physiological movements and deliver electrical stimuli to damaged bone or cells without an external power source. The crucial bone property is its piezoelectricity. Bones can generate electrical charges and potential in response to mechanical stimuli, as they influence bone growth and regeneration. Piezoelectric materials respond to human microenvironment stimuli and are an important factor in bone regeneration and repair. This manuscript is an overview of the fundamentals of the materials generating the piezoelectric effect and their influence on bone repair and regeneration. This paper focuses on the state of the art of piezoelectric materials, such as polymers, ceramics, and composites, and their application in bone tissue engineering. We present important information from the point of view of bone tissue engineering. We highlight promising upcoming approaches and new generations of piezoelectric materials.

Keywords:
piezoelectricity, scaffolds, smart scaffolds, PVDF, PLLA, PVDF-TRFE, collagen, keratin, tissue engineering, bone tissue engineering, smart medicine, regenerative medicine

Moczulska-Heljak M., Heljak M., Sajkiewicz P. Ł., Kołbuk-Konieczny D., Unraveling hierarchically ordered melt electro-written tissue engineering scaffolds: Morphological and mechanical insights, POLYMER, ISSN: 0032-3861, DOI: 10.1016/j.polymer.2024.127717, Vol.313, pp.127717-1-9, 2024

Abstract:
Addressing critical tissue defects treatment remains a pressing challenge in medicine and bioengineering. Tissue engineering (TE) scaffolds, characterized by porous architectures suitable to cell growth, is a pivotal solution. Recent advances in additive techniques have revolutionized scaffold fabrication, enabling precise control over complex porous structures. This study conducts a comprehensive analysis of hierarchically ordered melt electrospun written (MEW) TE scaffolds, elucidating the relationships between fabrication parameters and their morphological and mechanical properties. Leveraging the phenomenon of melt jet deposit buckling, characteristic hierarchically ordered porous architectures were attained. The study explores the fabrication potential of hierarchically ordered porous MEW architectures across varied voltages, feed rates, and needle sizes. Morphometric parameters, including percent porosity, density of fiber intersections, and fiber diameter, were identified. It was revealed that for feed rates exceeding 20 mm/s, resultant fiber diameters were unaffected by voltage. However, increasing voltage leads to noticeable reduction of mesh stiffness due to the coiled fibers presence. Exceptions occur at the feed rate of 20 mm/s and for needle G24, where stiffness surpasses those of regular primary pattern, which could be attributed to increased number of fiber interconnections.

Keywords:
MEW, Hierarchically ordered meshes, Coiled architectures, Entangled meshes

Osial M., Ha G., Vu V., Nguyen P., Nieciecka D., Pietrzyk‑Thel P., Urbanek O., Olusegun S., Wilczewski S.^♦, Giersig M., Do H., Dinh T., One-pot synthesis of magnetic hydroxyapatite (SPION/HAp) for 5-fluorouracil delivery and magnetic hyperthermia, Journal of Nanoparticle Research, ISSN: 1388-0764, DOI: 10.1007/s11051-023-05916-x, Vol.26, No.7, pp.1-23, 2024

Abstract:
This work presents the synthesis and characterization of a composite made of superparamagnetic iron oxide and hydroxyapatite nanoparticles (SPION/HAp) with a well-developed surface for loading anticancer drugs and for use in magnetic hyperthermia and local chemotherapy. The proposed material was obtained by an easy one-pot co-precipitation method with a controlled ratio of SPION to HAp. The morphology was studied by SEM and TEM, indicating rod-like structures for high HAp content in the composite and granule-like structures with increasing SPION. Its crystallinity, elemental composition, and functional groups were determined by X-ray diffraction, EDS, and FT-IR, respectively. The nanocomposite was then stabilized with citrates (CA), polyethylene glycol (PEG), and folic acid (FA) as agents to improve intracellular absorption, while turbidimetric studies confirmed that only citrates effectively stabilized the magnetic carriers to form a colloidal suspension. Subsequently, 5-fluorouracil (5-FU) was loaded into the magnetic carriers and tested in vitro using the L-929 cell line. The studies showed no cytotoxicity of the citrate-stabilized suspension against fibroblasts and some cytotoxicity after 5-FU release. In addition to in vitro studies, the composite was also tested on biomimetic membranes made of DOPC, DOPE, cholesterol, and DOPS lipids using Langmuir trough. The results show that the resulting suspension interacts with biomimetic membranes, while magnetic hyperthermia studies confirm effective heat generation to achieve therapeutic 42–46 °C and improve drug release from magnetic carriers.

Keywords:
SPION, Hydroxyapatite, Magnetic hyperthermia, Drug delivery, 5-fluorouracil, Biomimetic membranes, Nanostructures, Cancer treatment