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The paper describes the type of changes in the structure and mechanical properties of 3D printed shapes under the influence of mineral oil. The effects of a room (23 °C) and elevated temperature (70 °C) on 3D prints manufactured by the FDM method and stored in oil for 15, 30, and 60 days on the change of properties and structure were investigated. The samples were produced from ABS (poly(acrylonitrile-co-butadiene-co-styrene)), ASA (poly(acrylonitrile-co-styrene-co-acrylate), PLA (poly(lactic acid)), and HIPS (high-impact polystyrene). Tests related to the strength of the materials, such as the static tensile test and Charpy impact test, were carried out. The structure was evaluated using a scanning electron microscope, and changes in chemical structure were determined by conducting FTIR (Fourier transform infrared spectroscopy) and TGA (thermogravimetric analysis) tests. The analysis of the results provided important information about the impact of mineral oil on specific materials. This is critical for designing and manufacturing components that can withstand mineral oil exposure in real-world environments. The materials underwent varying changes. Strength increased for PLA by about 28%, remained unchanged for ABS and HIPS during exposure for 30 days, and decreased for ASA with extended exposure up to 14%.
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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.
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The paper presents the results of testing the properties of wood-polymer composites (WPC) based on plasticised poly(vinyl chloride) (PVC-P). Materials with variable contents of wood filler (Arbocel C 320) or plasticiser (di-isononyl phthalate) were produced and then analysed. The share of wood flour in the material was up to 50 phr, and the plasticiser content was up to 40 phr. Functional properties, such as tensile properties, mechanical properties at variable temperature (DMTA), and water absorption, as well as processing properties such as rheological properties and analysis of the fusion process, were analysed. The influences of wood flour and plasticiser on the composites' properties in the solid and melted state were found. For example, with 40 phr of plasticiser, increasing the filler share from 0 phr to 50 phr resulted in an increased tensile modulus from 18 MPa to 274 MPa and viscosity at a share rate of 20 s-1, from 721 Pa·s to 1581 Pa·s. However, increasing the share of plasticiser from 20 phr to 40 phr with 30 phr of filler reduces the value of these properties from 1760 MPa to 112 MPa and from 2768 Pa·s to 1151 Pa·s, respectively. It was also found that increasing the share of wood flour in the composite noticeably reduces the effectiveness of the plasticiser.
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Chemical modification of the surface of halloysite nanotubes (HNT) by alkalization (with sodium hydroxide (NaOH)) and grafting with silanes (bis(trimethylsilyl)amine (HMDS)) was carried out. The efficiency of the alkalization and grafting process was evaluated by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and the nitrogen adsorption method were used. XRD and FTIR analysis confirmed the formation of bonds of trimethylsilyl groups to the HNT surface which changed the nature of the surface from hydrophilic to hydrophobic. In addition, it was noted that grafting with silanes decreases by 7.2% the specific surface area of the halloysite compared to the alkalized material. High-density polyethylene (HDPE) composites with halloysite (HNT), alkalized halloysite (alk-HNT), and HMDS-modified halloysite (m-HNT) were processed in the molten state in a Brabender mixer chamber. On SEM/EDS micrographs of HDPE composites with silanized HNT, a change in surface characteristics from smooth to ductile was observed. Higher melting point values based on differential scanning calorimetry (DSC) analysis of HDPE composites with 5%wt silanized halloysite in comparison with HNT and alk-HNT of, respectively, 2.2% and 1.4% were found, which indicates a slight beneficial influence of the filler on the quality of ordering of the crystalline phase of the matrix.
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3D printing technology is becoming a widely adopted alternative to traditional polymer manufacturing methods. The most important advantage of 3D printing over traditional manufacturing methods, such as injection molding or extrusion, is the short time from the creation of a new design to the finished product. Nevertheless, 3D-printed parts generally have lower strength and lower durability compared to the same parts manufactured using traditional methods. Resistance to the environmental conditions in which a 3D-printed part operates is important to its durability. One of the most important factors that reduces durability and degrades the mechanical properties of 3D-printed parts is temperature, especially rapid temperature changes. In the case of inhomogeneous internal geometry and heterogeneous material properties, rapid temperature changes can have a significant impact on the degradation of 3D-printed parts. This degradation is more severe in high-humidity environments. Under these complex service conditions, information on the strength and fatigue behavior of 3D-printed polymers is limited. In this study, we evaluated the effects of high humidity and temperature changes on the durability and strength properties of 3D-printed parts. Samples made of commonly available materials such as ABS (Acrylonitrile Butadiene Styrene), ASA (Acrylonitrile-Styrene-Acrylate), HIPS (High-Impact Polystyrene), and PLA (Poly(lactic acid)) were subjected to temperature cycling, from an ambient temperature to -20 °C, and then were heated to 70 °C. After thermal treatment, the samples were subjected to cyclic loading to determine changes in their fatigue life relative to non-thermally treated reference samples. The results of cyclic testing showed a decrease in durability for samples made of ASA and HIPS. The ABS material proved to be resistant to the environmental effects of shocks, while the PLA material exhibited an increase in durability. Changes in the internal structure and porosity of the specimens under temperature changes were also evaluated using microcomputed tomography (microCT). Temperature changes also affected the porosity of the samples, which varied depending on the material used.
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To date, there has been limited information in the literature on the application of carbon fibre-carbon nanotube systems for the modification of poly(vinyl chloride) (PVC) matrixes by micro- and nanometric fillers and an evaluation of the properties of the unique materials produced. This paper presents the results of newly designed unique multiscale composites. The advantages of the simultaneous use of carbon fibres (CFs) and carbon nanotubes (CNTs) in PVC modification are discussed. To increase the dispersibility of the nanofiller, CFs together with nanotubes were subjected to a sonication process. The resulting material was introduced into PVC blends, which were processed by extrusion. The ratio of components in the hybrid filler with CF_CNT was 20:1, and its proportion in the PVC matrix was 1, 5, and 10 wt.%, respectively. Comparatively, PVC composites modified only with carbon fibres were obtained. The structure, thermal, electrical, and mechanical properties and swelling resistance of the composites were studied. The study showed a favourable homogeneous dispersion of nanotubes in the PVC matrix. This enabled effective modification of the structure at the nanometric level and the formation of an interpenetrating network of well-dispersed hybrid filler, as evidenced by a decrease in volume resistivity and improvement in swelling resistance, as well as an increase in glass transition temperature in the case of PVC/CF_CNT composites.
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Three-dimensionally printed parts are increasingly used in industry for quick repairs. They are often operated in the presence of grease, oil, and others. This article describes the effect of engine mineral oil on the fatigue life of 3D-printed FDM plastic samples. For this reason, this article aimed to investigate the influence of oil on the fatigue life of materials made using this technology. Samples made of ABA, ASA, PLA, and HIPS materials were printed with 100% fill. Divided into groups, they were stored for 15, 30, and 60 days in an oil bath at a room temperature of 23 °C and an increased temperature of 70 °C. To compare the effect of storage in oil, static tests were performed to determine the tensile strength of the specimens and to determine the load levels for the cyclic tests. Cyclic tests were performed to determine the effect of oil and temperature on the fatigue life. Internal structure studies of the specimens were performed using computed microtomography to determine the changes in the porosity of the specimens under the influence of oil. In the case of ABS, the oil-bathed samples showed a clear increase in the fatigue life, especially at 23 °C. For the ASA specimens, an increase was also evident, especially for the lower stress value. For HIPS and PLA, no clear effect of the oil bath on the fatigue life value of the samples was determined. Porosity studies using computed microtomography showed a clear decrease in the porosity of the samples as a result of the oil bath for all of them.
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In this study, we conducted the first plasticization of wheat flour (WF) with the addition of choline chloride:urea (1:5 molar ratio) eutectic mixture as a plasticizer and spent coffee grounds (cf) as a filler. Thermoplastic wheat flour (TPWF) films were obtained via twin-screw extrusion and then thermocompression. Their physicochemical characterization included mechanical tests, dynamic mechanical thermal analysis (DMTA), and sorption tests. XRD analysis revealed that the eutectic plasticizer led to a high degree of WF amorphization, which affected the physicochemical properties of TPWF. The results indicated that it was easy for the TPWF biocomposites to undergo thermocompression even with a high amount of the filler (20 pph per flour). The addition of the cf into TPWF led to an increase in tensile strength and a decrease in the swelling degree of the biocomposites. Biodegradation tests in soil revealed that the materials wholly degraded within 11 weeks. Moreover, a study of cultivated plants indicated that the biocomposites did not exhibit a toxic influence on the model rowing plant.
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Beer is among the most popular beverages in the world, with the production distributed uniformly between the biggest continents, so the utilization of brewing by-products is essential on a global scale. Among their potential recipients, the plastics industry offers extensive range of potential products. Herein, the presented study investigated the application of currently underutilized solid brewing by-products (brewers' spent grain, spent hops, spent yeast) as fillers for highly-filled poly(ε-caprolactone)-based composites, providing the first direct connection between spent hops or spent yeast and the polymer composites. Comprehensive by-product characterization revealed differences in chemical composition. The elemental C:O ratio, protein content, and Trolox equivalent antioxidant capacity varied from 1.40 to 1.89, 12.9 to 32.4 wt%, and 2.41 to 10.24 mg/g, respectively, which was mirrored in the composites' structure and performance. Morphological analysis pointed to the composition-driven hydrophilicity gap limiting interfacial adhesion for high shares of brewers' spent grain and spent hops, due to high hydrophilicity induced by carbohydrate content. Phytochemicals and other components of applied by-products stimulated composites' oxidative resistance, shifting oxidation onset temperature from 261 °C for matrix over 360 °C for high spent yeast shares. Simultaneously, spent yeast also provided compatibilizing effects for poly(ε-caprolactone)-based composites, reducing complex viscosity compared to other fillers and indicating its highest affinity to poly(ε-caprolactone)due to the lowest hydrophilicity gap. The presented results indicate that the proper selection of brewing by-products and adjustment of their shares creates an exciting possibility of engineering composites' structure and performance, which can be transferred to other polymers differing with hydrophilicity.
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Humulus , Saccharomyces cerevisiae , Cerveza , Polímeros , Carbohidratos/análisis , Grano Comestible/químicaRESUMEN
Rapid economic growth implicated the developing multiple industry sectors, including the automotive branch, increasing waste generation since recycling and utilization methods have not been established simultaneously. A very severe threat is the generation of enormous amounts of post-consumer tires considered burdensome waste, e.g., due to the substantial emissions of volatile organic compounds (VOCs). Therefore, it is essential to develop novel, environmentally friendly methods for their utilization, which would hinder their environmental impacts. One of the most promising approaches is shredding, resulting in the generation of ground tire rubber (GTR), which can be introduced into polymeric materials as filler. The presented work is related to the thermomechanical treatment of GTR in a twin-screw extruder with zinc borate, whose incorporation is aimed to enhance shear forces within the extruder barrel. Modified GTR was introduced into flexible polyurethane (PU) foams, and the impact of modification parameters on the cellular structure, static and dynamic mechanical performance, thermal stability, as well as thermal insulation, and acoustic properties was investigated. Emissions of VOCs from applied fillers and prepared composites were monitored and evaluated. Depending on the treatment parameters, beneficial changes in foams' cellular structure were noted, which enhanced their thermal insulation performance, mechanical strength, and thermal stability. It was proven that the proposed method of GTR thermomechanical treatment assisted by zinc borate particles might benefit the performance of flexible PU foamed composites and hinder VOC emissions, which could broaden the application range of GTR and provide novel ways for its efficient utilization.
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Boratos , Goma , Poliuretanos , ZincRESUMEN
The purpose of this study was to modify plasticised PVC to obtain a material with antimicrobial properties and selected mechanical properties. Natural cassia oil (CO) was used to modify plasticised PVC materials. The modified material was produced by extrusion. The introduced modifier had a maximum concentration of 20 phr. Rheological and mechanical properties were evaluated, and the glass transition temperature was determined. The antioxidant and antimicrobial activity of the agar diffusion method was investigated by analysing the growth inhibition zones against Enterococcus faecalis and Listeria monocytogenes. A favourable effect of the cassia oil content on the increase in antioxidant activity of the developed polymeric materials was found with an increase in the modifier content and the duration of action (30 days). The largest growth restriction zones were observed for L. monocytogenes, i.e., they showed the highest sensitivity to the modified material. The simultaneous decrease in modulus of elasticity, increase in elongation at break, and decrease in Tg indicate that the modifier has a plasticising effect on PVC. The developed material may find application as an active and/or functional material, especially as an emitter of antimicrobial agents, in the packaging used to store minimally processed food.
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A large amount of graphene-related research is its use as a filler for polymer composites, including thin nanocomposite films. However, its use is limited by the need for large-scale methods to obtain high-quality filler, as well as its poor dispersion in the polymer matrix. This work presents polymer thin-film composites based on poly(vinyl chloride) (PVC) and graphene, whose surfaces were modified by curcuminoids. TGA, UV-vis, Raman spectroscopy, XPS, TEM, and SEM methods have confirmed the effectiveness of the graphene modification due to π-π interactions. The dispersion of graphene in the PVC solution was investigated by the turbidimetric method. SEM, AFM, and Raman spectroscopy methods evaluated the thin-film composite's structure. The research showed significant improvements in terms of graphene's dispersion (in solutions and PVC composites) following the application of curcuminoids. The best results were obtained for materials modified with compounds obtained from the extraction of the rhizome of Curcuma longa L. Modification of the graphene's surface with these compounds also increased the thermal and chemical stability of PVC/graphene nanocomposites.
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The rapidly growing production and usage of lithium-ion batteries (LIBs) dramatically raises the number of harmful wastes. Consequently, the LIBs waste management processes, taking into account reliability, efficiency, and sustainability criteria, became a hot issue in the context of environmental protection as well as the scarcity of metal resources. In this paper, we propose for the first time a functional material-a magnetorheological fluid (MRF) from the LIBs-based liquid waste containing heavy metal ions. At first, the spent battery waste powder was treated with acid-leaching, where the post-treatment acid-leaching solution (ALS) contained heavy metal ions including cobalt. Then, ALS was used during wet co-precipitation to obtain cobalt-doped superparamagnetic iron oxide nanoparticles (SPIONs) and as an effect, the harmful liquid waste was purified from cobalt. The obtained nanoparticles were characterized with SEM, TEM, XPS, and magnetometry. Subsequently, superparamagnetic nanoparticles sized 15 nm average in diameter and magnetization saturation of about 91 emu g-1 doped with Co were used to prepare the MRF that increases the viscosity by about 300% in the presence of the 100 mT magnetic fields. We propose a facile and cost-effective way to utilize harmful ALS waste and use them in the preparation of superparamagnetic particles to be used in the magnetorheological fluid. This work describes for the first time the second life of the battery waste in the MRF and a facile way to remove the harmful ingredients from the solutions obtained after the acid leaching of LIBs as an effective end-of-life option for hydrometallurgical waste utilization.
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The article presents the research results on the influence of variable shock conditions, such as temperature and water, thus reflecting shock atmospheric conditions during freezing and thawing, on the properties of samples produced using 3D printing technology from commonly used materials such as ABS, HIPS, PLA, and ASA. Understanding how different environmental conditions affect the quality, reliability, and durability of 3D prints can help to optimize the printing process and provide valuable information about their application possibilities. Tests related to the strength of the materials, such as static tensile testing, Charpy impact testing, and evaluation of structures, were carried out using a scanning electron microscope (SEM). Changes in chemical properties were measured by performing tests such as FTIR and TGA. Variations in chemical properties were measured by performing tests such as FTIR and TGA. One shock cycle lasting 7 days was sufficient to alter the properties of 3D prints, with the extent of changes depending on the material, as summarized in the test results.
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In this article, halloysite-lignin hybrid materials (HL) were designed and obtained. The weak hydrogen bonds found between the components were determined based on Fourier transform infrared spectroscopy (FTIR), proving the achievement of class I hybrid systems. The HL systems were characterized by very good thermal stability and relatively good homogeneity, which increased as the proportion of the inorganic part increased. This was confirmed by analyzing scanning electron microscope (SEM) images and assessing particle size distributions and polydispersity indexes. Processing rigid poly(vinyl chloride) (PVC) with HL systems with a content of up to 10 wt% in a Brabender torque rheometer allowed us to obtain composites with a relatively homogeneous structure confirmed by SEM observations; simultaneously, a reduction in the fusion time was noted. An improvement in PVC thermal stability of approximately 40 °C for composites with HL with a ratio of 1:5 wt/wt was noted. Regardless of the concentration of the HL system, PVC composites exhibited inconsiderably higher Young's modulus, but the incorporation of 2.5 wt% of fillers increased Charpy impact strength by 5-8 kJ/m2 and doubled elongation at break. This study demonstrated that favorable mechanical properties of PVC composites can be achieved, especially with an HL system with a ratio of 5:1 wt/wt.
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In this work, a method to increase the dispersion of graphene (GN) in the matrix of rigid poly(vinyl chloride) (PVC) by using a natural plant extract from Curcuma longa L. (CE) is proposed. Currently, despite the increasing number of reports on the improvement of GN dispersion in PVC blends, still there is a need to find environmentally friendly and economical dispersion stabilizers. We proposed a stabilizer that can be easily obtained from a plant offering thermal stability and high effectiveness. PVC/GN nanocomposites stabilized with the proposed extract were investigated by SEM, AFM (structure), TGA, and Congo red test (thermal properties). Additionally, static and dynamic mechanical properties and electrical resistivity were measured. The use of CE as a graphene dispersant improved its dispersion in the PVC matrix, influenced tensile properties, increased the storage modulus and glass transition temperature, and extended the thermal stability time of nanocomposites. In this work, a CE extract is proposed as an efficient eco-friendly additive for the production of nanocomposites with an improved homogeneity of a nanofiller in the matrix and promising characteristics.
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Grafito , Nanocompuestos , Cloruro de Vinilo , Grafito/química , Curcuma , Rizoma , Cloruro de Polivinilo/química , Nanocompuestos/química , Extractos VegetalesRESUMEN
The paper presents the characteristics of unplasticized PVC composites modified with biofiller obtained from the waste eggshells of hen eggs. The composites obtained by extrusion contained from 10 phr to 40 phr of biofiller. The filler was characterized using the SEM, TG, and sieve analysis methods. The influence of the filler on the processing properties was determined using plastographometric and MFR tests. Fundamental analysis of mechanical properties was also performed, i.e., Charpy impact strength and determination of tensile properties. The mechanical properties were supported with dynamical mechanical thermal analysis, time of thermal stability, and thermogravimetric analysis. Structure analysis was also performed using SEM and X-ray microcomputed tomography (micro-CT). The processing properties of the tested composites do not give grounds for disqualifying such material from traditional processing PVC mixtures. Notably, the biofiller significantly improves thermal stability. Ground eggshells (ES) work as scavengers for the Cl radicals released in the first stage, which delays the PVC chain's decay. Additionally, a significant increase in the value of the modulus of elasticity and softening point (VST) of the composites concerning PVC was found. Ground hen eggshells can be used as an effective filler for PVC composites.
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Rotational molding is a technology in which polymeric thin-walled products can be made. The newest descriptions of this technology concern the possibility of obtaining polymer composite materials. There are two main methods of incorporating fillers into a polymer matrix. Dry blending is based on mixing fillers with polymer powders before rotational molding by hand or using automatic mixers. In the melt compounding method, fillers are mixed with the polymer in the preliminary step by melt processing and then grinding or pulverization to obtain polymer powders for rotational molding. This work aimed to investigate the impact of the processing procedure on the structure and properties of biobased composites with expanded vermiculite. Produced rotomolded parts were examined using mechanical tests to assess changes in tensile, flexural, and impact properties. The most significant difference in mechanical properties was noted for samples with 10 wt% expanded vermiculite (EV). The elasticity modulus increases by almost 2 fold when the sample is prepared in a two-step process, the tensile strength is 4-fold higher, the flexural modulus is 3-fold higher, and the flexural strength is 5-fold higher. We also investigated thermomechanical properties in DMA measurement. The void volume content was also measured to control the quality of obtained parts. The porosity of dry blended samples containing more than 2 wt% EV is almost 2-fold higher. Other methods to control quality and structure were optical and scanning electron microscopy used for rotomolded parts and polymer powders. The investigations of rotomolded parts were supplemented with a complete description of used materials, including the particle size distributions of polymer powders and filler. Analysis of the thermal properties and chemical structure was also performed despite all the mechanical tests. The emerging conclusions from the research clearly show that the two-step process allows for achieving a more beneficial mechanical performance of the composites made of the biobased polymer in rotational molding technology.
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The development of additive manufacturing methods known as "3D printing" started in the 1980s. In these methods, spatial models are created from a semi-finished product such as a powder, filament or liquid. The model is most often created in layers, which are created from the semi-finished product, which is most often subjected to thermal treatment or using light or ultraviolet rays. The technology of additive manufacturing has both advantages and disadvantages when compared to the traditionally used methods of processing thermoplastic materials, such as, for example, injection or extrusion. The most important advantages are low cost, flexibility and speed of manufacturing of elements with different spatial shapes. From the point of view of the user of the product, the most important disadvantages are the lower mechanical properties and lower resistance to environmental factors that occur during the use of the manufactured products. The purpose of this review is to present current information and a compilation of features in the field of research on the effects of the interactions of different types of environments on the mechanical properties of 3D-manufactured thermoplastic products. Changes in the structure and mechanical properties of the material under the influence of factors such as humidity, salt, temperature, UV rays, gasoline and the environment of the human body are presented. The presented article enables the effects of environmental conditions on common materials used in 3D printing technology to be collated in one place.
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This article presents the results of studies of poly(vinyl chloride) (PVC) composites modified with a hybrid carbon filler of carbon fibres (CFs) and multiwalled carbon nanotubes (MWCNTs). The hybrid filler was produced by a solvent method, using poly(vinyl acetate) (PVAc) as an adhesive. The proportion of components in the hybrid filler with CF-CNT-PVAc was 50:2.5:1, respectively. The obtained hybrid filler was evaluated by SEM, TG, and Raman spectroscopy. The PVC composites were produced by extrusion with proportions of the hybrid filler as 1 wt%, 5 wt%, or 10 wt%. Thermal stability by the TG method, mechanical properties, and the glass transition temperature (Tg) by the DMA and DSC methods were determined. The composite structure was evaluated by SEM and Raman spectroscopy. The effect of the hybrid filler on electrical properties was investigated by studying the cross and surface resistivity. It was concluded that, aside from a substantial increase in the elastic modulus, no substantial improvement in the PVC/CF/CNT composites' mechanical properties was observed; however, slight increases in thermal stability and Tg were noted. The addition of the hybrid filler contributed to a substantial change in the composites' electrical properties. SEM observations demonstrated improved CNT dispersibility in the matrix, however, without a completely homogeneous coverage of CF by CNT.