Research

11 pages, 2301 KiB

Open AccessArticle

Conversion of Polyethylene to Low-Molecular-Weight Oil Products at Moderate Temperatures Using Nickel/Zeolite Nanocatalysts

by Hyungjin Cho, Ahyeon Jin, Sun Ju Kim, Youngmin Kwon, Eunseo Lee, Jaeman J. Shin and Byung Hyo Kim

Materials 2024, 17(8), 1863; https://doi.org/10.3390/ma17081863 - 18 Apr 2024

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Abstract

Polyethylene (PE) is the most widely used plastic, known for its high mechanical strength and affordability, rendering it responsible for ~70% of packaging waste and contributing to microplastic pollution. The cleavage of the carbon chain can induce the conversion of PE wastes into [...] Read more.

Polyethylene (PE) is the most widely used plastic, known for its high mechanical strength and affordability, rendering it responsible for ~70% of packaging waste and contributing to microplastic pollution. The cleavage of the carbon chain can induce the conversion of PE wastes into low-molecular-weight hydrocarbons, such as petroleum oils, waxes, and natural gases, but the thermal degradation of PE is challenging and requires high temperatures exceeding 400 °C due to its lack of specific chemical groups. Herein, we prepare metal/zeolite nanocatalysts by incorporating small-sized nickel nanoparticles into zeolite to lower the degradation temperature of PE. With the use of nanocatalysts, the degradation temperature can be lowered to 350 °C under hydrogen conditions, compared to the 400 °C required for non-catalytic pyrolysis. The metal components of the catalysts facilitate hydrogen adsorption, while the zeolite components stabilize the intermediate radicals or carbocations formed during the degradation process. The successful pyrolysis of PE at low temperatures yields valuable low-molecular-weight oil products, offering a promising pathway for the upcycling of PE into higher value-added products. Full article

(This article belongs to the Special Issue Advances in Polymer Blends and Composites)

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24 pages, 7943 KiB

Open AccessArticle

Electrical and Electro-Thermal Characteristics of (Carbon Black-Graphite)/LLDPE Composites with PTC Effect

by Eduard-Marius Lungulescu, Cristina Stancu, Radu Setnescu, Petru V. Notingher and Teodor-Adrian Badea

Materials 2024, 17(5), 1224; https://doi.org/10.3390/ma17051224 - 06 Mar 2024

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Abstract

Electrical properties and electro-thermal behavior were studied in composites with carbon black (CB) or hybrid filler (CB and graphite) and a matrix of linear low-density polyethylene (LLDPE). LLDPE, a (co)polymer with low crystallinity but with high structural regularity, was less studied for Positive [...] Read more.

Electrical properties and electro-thermal behavior were studied in composites with carbon black (CB) or hybrid filler (CB and graphite) and a matrix of linear low-density polyethylene (LLDPE). LLDPE, a (co)polymer with low crystallinity but with high structural regularity, was less studied for Positive Temperature Coefficient (PTC) applications, but it would be of interest due to its higher flexibility as compared to HDPE. Structural characterization by scanning electron microscopy (SEM) confirmed a segregated structure resulted from preparation by solid state powder mixing followed by hot molding. Direct current (DC) conductivity measurements resulted in a percolation threshold of around 8% (w) for CB/LLDPE composites. Increased filler concentrations resulted in increased alternating current (AC) conductivity, electrical permittivity and loss factor. Resistivity-temperature curves indicate the dependence of the temperature at which the maximum of resistivity is reached (T_max(R)) on the filler concentration, as well as a differentiation in the T_max(R) from the crystalline transition temperatures determined by DSC. These results suggest that crystallinity is not the only determining factor of the PTC mechanism in this case. This behavior is different from similar high-crystallinity composites, and suggests a specific interaction between the conductive filler and the polymeric matrix. A strong dependence of the PTC effect on filler concentration and an optimal concentration range between 14 and 19% were also found. Graphite has a beneficial effect not only on conductivity, but also on PTC behavior. Temperature vs. time experiments, revealed good temperature self-regulation properties and current and voltage limitation, and irrespective of the applied voltage and composite type, the equilibrium superficial temperature did not exceed 80 °C, while the equilibrium current traversing the sample dropped from 22 mA at 35 V to 5 mA at 150 V, proving the limitation capacities of these materials. The concentration effects revealed in this work could open new perspectives for the compositional control of both the self-limiting and interrupting properties for various low-temperature applications. Full article

(This article belongs to the Special Issue Advances in Polymer Blends and Composites)

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27 pages, 9708 KiB

Open AccessArticle

Preparation and Characterization of Composites Based on ABS Modified with Polysiloxane Derivatives

by Bogna Sztorch, Roksana Konieczna, Daria Pakuła, Miłosz Frydrych, Bogdan Marciniec and Robert E. Przekop

Materials 2024, 17(3), 561; https://doi.org/10.3390/ma17030561 - 24 Jan 2024

Viewed by 595

Abstract

In this study, organosilicon compounds were used as modifiers of filaments constituting building materials for 3D printing technology. Polymethylhydrosiloxane underwent a hydrosilylation reaction with styrene, octadecene, and vinyltrimethoxysilane to produce new di- or tri-functional derivatives with varying ratios of olefins. These compounds were [...] Read more.

In this study, organosilicon compounds were used as modifiers of filaments constituting building materials for 3D printing technology. Polymethylhydrosiloxane underwent a hydrosilylation reaction with styrene, octadecene, and vinyltrimethoxysilane to produce new di- or tri-functional derivatives with varying ratios of olefins. These compounds were then mixed with silica and incorporated into the ABS matrix using standard processing methods. The resulting systems exhibited changes in their physicochemical and mechanical characteristics. Several of the obtained composites (e.g., modified with VT:6STYR) had an increase in the contact angle of over 20° resulting in a hydrophobic surface. The addition of modifiers also prevented a decrease in rheological parameters regardless of the amount of filler added. In addition, comprehensive tests of the thermal decomposition of the obtained composites were performed and an attempt was made to precisely characterize the decomposition of ABS using FT-IR and optical microscopy, which allowed us to determine the impact of individual groups on the thermal stability of the system. Full article

(This article belongs to the Special Issue Advances in Polymer Blends and Composites)

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19 pages, 7943 KiB

Open AccessArticle

A Comparative Study between Blended Polymers and Copolymers as Emitting Layers for Single-Layer White Organic Light-Emitting Diodes

by Despoina Tselekidou, Kyparisis Papadopoulos, Vasileios Foris, Vasileios Kyriazopoulos, Konstantinos C. Andrikopoulos, Aikaterini K. Andreopoulou, Joannis K. Kallitsis, Argiris Laskarakis, Stergios Logothetidis and Maria Gioti

Materials 2024, 17(1), 76; https://doi.org/10.3390/ma17010076 - 23 Dec 2023

Viewed by 983

Abstract

Extensive research has been dedicated to the solution-processable white organic light-emitting diodes (WOLEDs), which can potentially influence future solid-state lighting and full-color flat-panel displays. The proposed strategy based on WOLEDs involves blending two or more emitting polymers or copolymerizing two or more emitting [...] Read more.

Extensive research has been dedicated to the solution-processable white organic light-emitting diodes (WOLEDs), which can potentially influence future solid-state lighting and full-color flat-panel displays. The proposed strategy based on WOLEDs involves blending two or more emitting polymers or copolymerizing two or more emitting chromophores with different doping concentrations to produce white light emission from a single layer. Toward this direction, the development of blends was conducted using commercial blue poly(9,9-di-n-octylfluorenyl2,7-diyl) (PFO), green poly(9,9-dioctylfluorenealt-benzothiadiazole) (F8BT), and red spiro-copolymer (SPR) light-emitting materials, whereas the synthesized copolymers were based on different chromophores, namely distyryllanthracene, distyrylcarbazole, and distyrylbenzothiadiazole, as yellow, blue, and orange–red emitters, respectively. A comparative study between the two approaches was carried out to examine the main challenge for these doping systems, which is ensuring the proper balance of emissions from all the units to span the entire visible range. The emission characteristics of fabricated WOLEDs will be explored in terms of controlling the emission from each emitter, which depends on two possible mechanisms: energy transfer and carrier trapping. The aim of this work is to achieve pure white emission through the color mixing from different emitters based on different doping concentrations, as well as color stability during the device operation. According to these aspects, the WOLED devices based on the copolymers of two chromophores exhibit the most encouraging results regarding white color emission coordinates (0.28, 0.31) with a CRI value of 82. Full article

(This article belongs to the Special Issue Advances in Polymer Blends and Composites)

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16 pages, 4172 KiB

Open AccessArticle

Exploration of Methodologies for Developing Antimicrobial Fused Filament Fabrication Parts

by Sotirios Pemas, Eleftheria Xanthopoulou, Zoi Terzopoulou, Georgios Konstantopoulos, Dimitrios N. Bikiaris, Christine Kottaridi, Dimitrios Tzovaras and Eleftheria Maria Pechlivani

Materials 2023, 16(21), 6937; https://doi.org/10.3390/ma16216937 - 29 Oct 2023

Viewed by 990

Abstract

Composite 3D printing filaments integrating antimicrobial nanoparticles offer inherent microbial resistance, mitigating contamination and infections. Developing antimicrobial 3D-printed plastics is crucial for tailoring medical solutions, such as implants, and cutting costs when compared with metal options. Furthermore, hospital sustainability can be enhanced via [...] Read more.

Composite 3D printing filaments integrating antimicrobial nanoparticles offer inherent microbial resistance, mitigating contamination and infections. Developing antimicrobial 3D-printed plastics is crucial for tailoring medical solutions, such as implants, and cutting costs when compared with metal options. Furthermore, hospital sustainability can be enhanced via on-demand 3D printing of medical tools. A PLA-based filament incorporating 5% TiO₂ nanoparticles and 2% Joncryl as a chain extender was formulated to offer antimicrobial properties. Comparative analysis encompassed PLA 2% Joncryl filament and a TiO₂ coating for 3D-printed specimens, evaluating mechanical and thermal properties, as well as wettability and antimicrobial characteristics. The antibacterial capability of the filaments was explored after 3D printing against Gram-positive Staphylococcus aureus (S. aureus, ATCC 25923), as well as Gram-negative Escherichia coli (E. coli, ATCC 25922), and the filaments with 5 wt.% embedded TiO₂ were found to reduce the viability of both bacteria. This research aims to provide the optimal approach for antimicrobial and medical 3D printing outcomes. Full article

(This article belongs to the Special Issue Advances in Polymer Blends and Composites)

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22 pages, 2731 KiB

Open AccessArticle

Influence Analysis of Modified Polymers as a Marking Agent for Material Tracing during Cyclic Injection Molding

by Tom Eggers, Sonja Marit Blumberg, Frank von Lacroix, Werner Berlin and Klaus Dröder

Materials 2023, 16(18), 6304; https://doi.org/10.3390/ma16186304 - 20 Sep 2023

Viewed by 647

Abstract

Injection molding (IM) is already an established technology for manufacturing polymer products. However, in the course of the increased use of recyclates for economic and ecological reasons, its application capability has been confronted with new requirements for reliability and reproducibility. In addition, the [...] Read more.

Injection molding (IM) is already an established technology for manufacturing polymer products. However, in the course of the increased use of recyclates for economic and ecological reasons, its application capability has been confronted with new requirements for reliability and reproducibility. In addition, the IM process is confronted with regulations regarding a verifiable recycling degree in polymers. With regard to the material identification and storage of manufacturer-, process- or product-related data in polymers, the implementation of a material-inherent marking technology forms a potential answer. The IM process combined with modified polymers (MP) as a marking technology turns out to be a feasible approach to manufacturing reproducibly and offers a high quality based on increased process awareness and fulfilling the required traceability. Therefore, this work focuses on the trial evaluation of MP within the IM process. The influence of MP on the material process behavior and mechanical and thermal component properties, as well as the influence of the IM process and recycling on MP traceability, are investigated. No discernible influences of MP on the investigated properties could be identified, and the traceability from the initial material to a recyclate could be confirmed. MP is suitable for monitoring the aging state of polymers in IM. Full article

(This article belongs to the Special Issue Advances in Polymer Blends and Composites)

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17 pages, 31303 KiB

Open AccessArticle

Evaluation of Piezoresistive and Electrical Properties of Conductive Nanocomposite Based on Castor-Oil Polyurethane Filled with MWCNT and Carbon Black

by Diego S. Melo, Idalci C. Reis, Júlio C. Queiroz, Cicero R. Cena, Bacus O. Nahime, José A. Malmonge and Michael J. Silva

Materials 2023, 16(8), 3223; https://doi.org/10.3390/ma16083223 - 19 Apr 2023

Viewed by 1083

Abstract

Flexible films of a conductive polymer nanocomposite-based castor oil polyurethane (PUR), filled with different concentrations of carbon black (CB) nanoparticles or multiwall carbon nanotubes (MWCNTs), were obtained by a casting method. The piezoresistive, electrical, and dielectric properties of the PUR/MWCNT and PUR/CB composites [...] Read more.

Flexible films of a conductive polymer nanocomposite-based castor oil polyurethane (PUR), filled with different concentrations of carbon black (CB) nanoparticles or multiwall carbon nanotubes (MWCNTs), were obtained by a casting method. The piezoresistive, electrical, and dielectric properties of the PUR/MWCNT and PUR/CB composites were compared. The dc electrical conductivity of both PUR/MWCNT and PUR/CB nanocomposites exhibited strong dependences on the concentration of conducting nanofillers. Their percolation thresholds were 1.56 and 1.5 mass%, respectively. Above the threshold percolation level, the electrical conductivity value increased from 1.65 × 10⁻¹² for the matrix PUR to 2.3 × 10⁻³ and 1.24 × 10⁻⁵ S/m for PUR/MWCNT and PUR/CB samples, respectively. Due to the better CB dispersion in the PUR matrix, the PUR/CB nanocomposite exhibited a lower percolation threshold value, corroborated by scanning electron microscopy images. The real part of the alternating conductivity of the nanocomposites was in accordance with Jonscher’s law, indicating that conduction occurred by hopping between states in the conducting nanofillers. The piezoresistive properties were investigated under tensile cycles. The nanocomposites exhibited piezoresistive responses and, thus, could be used as piezoresistive sensors. Full article

(This article belongs to the Special Issue Advances in Polymer Blends and Composites)

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20 pages, 9290 KiB

Open AccessEditor’s ChoiceArticle

Polymer Composites with Self-Regulating Temperature Behavior: Properties and Characterization

by Radu Setnescu, Eduard-Marius Lungulescu and Virgil Emanuel Marinescu

Materials 2023, 16(1), 157; https://doi.org/10.3390/ma16010157 - 24 Dec 2022

Cited by 1 | Viewed by 1363

Abstract

A novel conductive composite material with homogeneous binary polymer matrix of HDPE (HD) and LLDPE (LLD), mixed with conductive filler consisting of carbon black (CB) and graphite (Gr), was tested against a HDPE composite with a similar conductive filler. Even the concentration of [...] Read more.

A novel conductive composite material with homogeneous binary polymer matrix of HDPE (HD) and LLDPE (LLD), mixed with conductive filler consisting of carbon black (CB) and graphite (Gr), was tested against a HDPE composite with a similar conductive filler. Even the concentration of the conductive filler was deliberately lower for (CB + Gr)/(LLD + HD), and the properties of this composite are comparable or better to those of (CB + Gr)/HD. The kinetic parameters of the ρ-T curves and from the DSC curves indicate that the resistivity peak is obtained when the polymer matrix is fully melted. When subjected to repeated thermal cycles, the composite (CB + Gr)/(LLD + HD) presented a better electrical behavior than composite CB + Gr)/HD, with an increase in resistivity (ρ_max) values with the number of cycles, as well as less intense NTC (Negative Temperature Coefficient) effects, both for the crosslinked and thermoplastic samples. Radiation crosslinking led to increased ρ_max values, as well as to inhibition of NTC effects in both cases, thus having a clear beneficial effect. Limitation effects of surface temperature and current intensity through the sample were observed at different voltages, enabling the use of these materials as self-regulating heating elements at various temperatures below the melting temperature. The procedure based on physical mixing of the components appears more efficient in imparting lower resistivity in solid state and high PTC (Positive Temperature Coefficient) effects to the composites. This effect is probably due to the concentration of the conductive particles at the surface of the polymer domains, which would facilitate the formation of the conductive paths. Further work is still necessary to optimize both the procedure of composite preparation and the properties of such materials. Full article

(This article belongs to the Special Issue Advances in Polymer Blends and Composites)

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13 pages, 3896 KiB

Open AccessArticle

Blown Composite Films of Low-Density/Linear-Low-Density Polyethylene and Silica Aerogel for Transparent Heat Retention Films and Influence of Silica Aerogel on Biaxial Properties

by Seong Baek Yang, Jungeon Lee, Sabina Yeasmin, Jae Min Park, Myung Dong Han, Dong-Jun Kwon and Jeong Hyun Yeum

Materials 2022, 15(15), 5314; https://doi.org/10.3390/ma15155314 - 02 Aug 2022

Cited by 1 | Viewed by 1664

Abstract

Blown films based on low-density polyethylene (LDPE)/linear low-density polyethylene (LLDPE) and silica aerogel (SA; 0, 0.5, 1, and 1.5 wt.%) were obtained at the pilot scale. Good particle dispersion and distribution were achieved without thermo oxidative degradation. The effects of different SA contents [...] Read more.

Blown films based on low-density polyethylene (LDPE)/linear low-density polyethylene (LLDPE) and silica aerogel (SA; 0, 0.5, 1, and 1.5 wt.%) were obtained at the pilot scale. Good particle dispersion and distribution were achieved without thermo oxidative degradation. The effects of different SA contents (0.5–1.5 wt.%) were studied to prepare transparent-heat-retention LDPE/LLDPE films with improved material properties, while maintaining the optical performance. The optical characteristics of the composite films were analyzed using methods such as ultraviolet–visible spectroscopy and electron microscopy. Their mechanical characteristics were examined along the machine and transverse directions (MD and TD, respectively). The MD film performance was better, and the 0.5% composition exhibited the highest stress at break. The crystallization kinetics of the LDPE/LLDPE blends and their composites containing different SA loadings were investigated using differential scanning calorimetry, which revealed that the crystallinity of LDPE/LLDPE was increased by 0.5 wt.% of well-dispersed SA acting as a nucleating agent and decreased by agglomerated SA (1–1.5 wt.%). The LDPE/LLDPE/SA (0.5–1.5 wt.%) films exhibited improved infrared retention without compromising the visible light transmission, proving the potential of this method for producing next-generation heat retention films. Moreover, these films were biaxially drawn at 13.72 MPa, and the introduction of SA resulted in lower draw ratios in both the MD and TD. Most of the results were explained in terms of changes in the biaxial crystallization caused by the process or the influence of particles on the process after a systematic experimental investigation. The issues were strongly related to the development of blown nanocomposites films as materials for the packaging industry. Full article

(This article belongs to the Special Issue Advances in Polymer Blends and Composites)

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21 pages, 8448 KiB

Open AccessArticle

Stability Study of the Irradiated Poly(lactic acid)/Styrene Isoprene Styrene Reinforced with Silica Nanoparticles

by Ana Maria Lupu (Luchian), Marius Mariş, Traian Zaharescu, Virgil Emanuel Marinescu and Horia Iovu

Materials 2022, 15(14), 5080; https://doi.org/10.3390/ma15145080 - 21 Jul 2022

Cited by 1 | Viewed by 1615

Abstract

In this paper, the stability improvement of poly(lactic acid) (PLA)/styrene-isoprene block copolymer (SIS) loaded with silica nanoparticles is characterized. The protection efficiency in the material of thermal stability is mainly studied by means of high accurate isothermal and nonisothermal chemiluminescence procedures. The oxidation [...] Read more.

In this paper, the stability improvement of poly(lactic acid) (PLA)/styrene-isoprene block copolymer (SIS) loaded with silica nanoparticles is characterized. The protection efficiency in the material of thermal stability is mainly studied by means of high accurate isothermal and nonisothermal chemiluminescence procedures. The oxidation induction times obtained in the isothermal CL determinations increase from 45 min to 312 min as the polymer is free of silica or the filler loading is about 10%, respectively. The nonisothermal measurements reveal the values of onset oxidation temperatures with about 15% when the concentration of SiO₂ particles is enhanced from none to 10%. The curing assay and Charlesby–Pinner representation as well as the modifications that occurred in the FTIR carbonyl band at 1745 cm⁻¹ are appropriate proofs for the delay of oxidation in hybrid samples. The improved efficiency of silica during the accelerated degradation of PLA/SIS 30/n-SiO₂ composites is demonstrated by means of the increased values of activation energy in correlation with the augmentation of silica loading. While the pristine material is modified by the addition of 10% silica nanoparticles, the activation energy grows from 55 kJ mol⁻¹ to 74 kJ mol⁻¹ for nonirradiated samples and from 47 kJ mol⁻¹ to 76 kJ mol⁻¹ for γ-processed material at 25 kGy. The stabilizer features are associated with silica nanoparticles due to the protection of fragments generated by the scission of hydrocarbon structure of SIS, the minor component, whose degradation fragments are early converted into hydroperoxides rather than influencing depolymerization in the PLA phase. The reduction of the transmission values concerning the growing reinforcement is evidence of the capacity of SiO₂ to minimize the changes in polymers subjected to high energy sterilization. The silica loading of 10 wt% may be considered a proper solution for attaining an extended lifespan under the accelerated degradation caused by the intense transfer of energy, such as radiation processing on the polymer hybrid. Full article

(This article belongs to the Special Issue Advances in Polymer Blends and Composites)

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15 pages, 8253 KiB

Open AccessArticle

A Comparative Study of Several Properties of Plywood Bonded with Virgin and Recycled LDPE Films

by Pavlo Bekhta, Antonio Pizzi, Iryna Kusniak, Nataliya Bekhta, Orest Chernetskyi and Arif Nuryawan

Materials 2022, 15(14), 4942; https://doi.org/10.3390/ma15144942 - 15 Jul 2022

Cited by 7 | Viewed by 1797

Abstract

In this work, to better understand the bonding process of plastic plywood panels, the effects of recycled low-density polyethylene (rLDPE) film of three thicknesses (50, 100, and 150 µm) and veneers of four various wood species (beech, birch, hornbeam, and poplar) on the [...] Read more.

In this work, to better understand the bonding process of plastic plywood panels, the effects of recycled low-density polyethylene (rLDPE) film of three thicknesses (50, 100, and 150 µm) and veneers of four various wood species (beech, birch, hornbeam, and poplar) on the properties of panels were studied. The obtained properties were also compared with the properties of plywood panels bonded by virgin low-density polyethylene (LDPE) film. The results showed that properties of plywood samples bonded with rLDPE and virgin LDPE films differ insignificantly. Samples bonded with rLDPE film demonstrated satisfactory physical and mechanical properties. It was also established that the best mechanical properties of plywood are provided by beech veneer and the lowest by poplar veneer. However, poplar plywood had the best water absorption and swelling thickness, and the bonding strength at the level of birch and hornbeam plywood. The properties of rLDPE-bonded plywood improved with increasing the thickness of the film. The panels bonded with rLDPE film had a close-to-zero formaldehyde content (0.01–0.10 mg/m²·h) and reached the super E0 emission class that allows for defining the laboratory-manufactured plastic-bonded plywood as an eco-friendly composite. Full article

(This article belongs to the Special Issue Advances in Polymer Blends and Composites)

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8 pages, 1076 KiB

Open AccessCommunication

Milling Parameter Optimization of Continuous-Glass-Fiber-Reinforced-Polypropylene Laminate

by Hanjie Hu, Bing Du, Conggang Ning, Xiaodong Zhang, Zhuo Wang, Yangyang Xiong, Xianjun Zeng and Liming Chen

Materials 2022, 15(7), 2703; https://doi.org/10.3390/ma15072703 - 06 Apr 2022

Cited by 1 | Viewed by 1824

Abstract

The composite-material laminate structure will inevitably encounter connection problems in use. Among them, mechanical connections are widely used in aerospace, automotive and other fields because of their high connection efficiency and reliable connection performance. Milling parameters are important for the opening quality. In [...] Read more.

The composite-material laminate structure will inevitably encounter connection problems in use. Among them, mechanical connections are widely used in aerospace, automotive and other fields because of their high connection efficiency and reliable connection performance. Milling parameters are important for the opening quality. In this paper, continuous-glass-fiber-reinforced-polypropylene (GFRPP) laminates were chosen to investigate the effects of different cutters and process parameters on the hole quality. The delamination factor and burr area were taken as the index to characterize the opening quality. After determining the optimal milling tool, the process window was obtained according to the appearance of the milling hole. In the selected process parameter, the maximum temperature did not reach the PP melting temperature. The best hole quality was achieved when the spindle speed was 18,000 r/min and the feed speed was 1500 mm/min with the corn milling cutter. Full article

(This article belongs to the Special Issue Advances in Polymer Blends and Composites)

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