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Biodegradable polymers have recently become attractive and have been increasingly used as matrix materials to replace fossil plastics due to concerns about the environmental issue. However, their application areas are limited due to their high costs and natural properties. In this study, we fabricated ecofriendly and economical polybutylene adipate terephthalate (PBAT) composites loaded with various concentrations of wood flour (WF) to investigate the effects on the PBAT and WF interfaces as well as the physical properties of the WF/PBAT biocomposites. Then, WF was acetylated with acetic anhydride, and the effect of WF acetylation on the mechanical and thermal properties of the biocomposites were investigated. The results showed that the tensile strength, tensile modulus, flexural strength and flexural modulus increased with WF loading in the composites, and acetylation could not only further increase these properties, but also increase the impact strength and elongation at break. The incorporation of WF would weaken the thermal stability of PBAT, but the thermal stability of the biocomposite could be improved after WF acetylation. The cold crystallization temperature and hydrophobicity of the WF/PBAT samples would be increased with the increasing load of the WF, while the melting enthalpy and the crystallinity of the samples reduced gradually. A morphological analysis of the modified composites revealed that the matrix exhibited greater interfacial interactions with the WF compared to the WF/PBAT. Considering the much lower cost of WF compared to PBAT, the improved properties of WF/PBAT biocomposites will make it economically competitive with other commercial polymers, and these biocomposites should have much wider application areas.
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In order to develop a new kind of filament material for the fused deposition modeling (FDM) 3D printing, the residue of Astragalus (ROA), one of the most important Chinese herbal medicines, and polylactic acid were chosen as the raw materials to FDM 3D print biomass composite specimens, the effects of the printing parameters on the properties of the specimens were investigated. The results indicated that the mechanical properties and thermal stability of the printed specimen were affected obviously by the parameters while the melting and crystallization behavior of the specimens were little affected. For the wettability, it was also little affected by the printing parameter except for the printing speed. Increasing the printing temperature and the filling density or reducing the printing speed and the layer thickness could improve both the mechanical properties and the thermal stability of the FDM 3D printed PLA/ROA composite specimen; reducing the deposition angle could also improve the mechanical properties while having little effect on the thermal stability of the specimen.
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Poliésteres , Impresión Tridimensional , Biomasa , Poliésteres/química , TemperaturaRESUMEN
In order to improve the properties of wood flour (WF)/poly(lactic acid) (PLA) 3D-printed composites, WF was treated with a silane coupling agent (KH550) and acetic anhydride (Ac2O), respectively. The effects of WF modification and the addition of acrylicester resin (ACR) as a toughening agent on the flowability of WF/PLA composite filament and the mechanical, thermal, dynamic mechanical thermal and water absorption properties of fused deposition modeling (FDM) 3D-printed WF/PLA specimens were investigated. The results indicated that the melt index (MI) of the specimens decreased after WF pretreatment or the addition of ACR, while the die swell ratio increased; KH550-modified WF/PLA had greater tensile strength, tensile modulus and impact strength, while Ac2O-modified WF/PLA had greater tensile modulus, flexural strength, flexural modulus and impact strength than unmodified WF/PLA; after the addition of ACR, all the strengths and moduli of WF/PLA could be improved; after WF pretreatment or the addition of ACR, the thermal decomposition temperature, storage modulus and glass transition temperature of WF/PLA were all increased, and water absorption was reduced.
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Harina , Madera , Poliésteres , Impresión Tridimensional , AguaRESUMEN
To develop a new kind of environment-friendly composite filament for fused deposition modeling (FDM) 3D printing, rice straw powder (RSP)/poly(lactic acid) (PLA) biocomposites were FDM-3D-printed, and the effects of the particle size and pretreatment of RSP on the properties of RSP/PLA biocomposites were investigated. The results indicated that the 120-mesh RSP/PLA biocomposites (named 120#RSP/PLA) showed better performance than RSP/PLA biocomposites prepared with other RSP sizes. Infrared results showed that pretreatment of RSP by different methods was successful, and scanning electron microscopy indicated that composites prepared after pretreatment exhibited good interfacial compatibility due to a preferable binding force between fiber and matrix. When RSP was synergistically pretreated by alkaline and ultrasound, the composite exhibited a high tensile strength, tensile modulus, flexural strength, and flexural modulus of 58.59, 568.68, 90.32, and 3218.12 MPa, respectively, reflecting an increase of 31.19%, 16.48%, 18.75%, and 25.27%, respectively, compared with unmodified 120#RSP/PLA. Pretreatment of RSP also improved the thermal stability and hydrophobic properties, while reducing the water absorption of 120#RSP/PLA. This work is believed to provide highlights of the development of cost-effective biocomposite filaments and improvement of the properties of FDM parts.
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Materiales Biocompatibles/química , Lignina/química , Poliésteres/química , Materiales Biocompatibles/economía , Análisis Costo-Beneficio , Ensayo de Materiales , Fenómenos Mecánicos , Microscopía Electrónica de Rastreo , Oryza , Tamaño de la Partícula , Polímeros/química , Polvos , Presión , Impresión Tridimensional , Estrés Mecánico , Temperatura , Resistencia a la Tracción , TermogravimetríaRESUMEN
Montmorillonite (MMT) is a natural mineral that has great potential as reinforcing filler in wood adhesives. In order to study the reinforcing mechanism more clearly, organic MMT-reinforced urea-formaldehyde adhesive (UF-OMMT) was prepared to analyze its chemical properties and crystal structure with Fourier Transform Infrared Spectroscopy (FTIR) and X-Ray Diffraction (XRD). The nanomechanical properties of UF, UF-MMT and PF-OMMT adhesives in the interphase of wood-based composite were analyzed by nanoindentation (NI) and the macro-bonding strength of composite were also tested. The results of FTIR and XRD indicated that in the spectra of MMT modified by cetyltrimethyl ammonium bromide (CTAB), the new peaks appeared at 2 929 and 2 853 cm-1corresponding to CH stretching vibrations of the organic intercalation agent (CTAB). The (001) diffraction peak of MMT was shifted to a lower angle and the lamellar repeat distance increases from 1.51 nm to 2.71 nm after organic modification. The ion exchange of the cations in montmorillonite with organic ammonium ions and the separating and disorder crystalline improved the compatibility of the modified clay with the polymers and the dispersion of the layers into the matrix. The good physical filling of MMT particles and the elastomer formed during the reaction could transfer and distribute loads between components more homogenously, therebycontributing to the improved mechanical properties of adhesives. As compared to the untreated UF, the reduced elastic modulus and hardness of UF-OMMT in the interphase increased by about 66.9% and 24.2%, respectively. At the macroscale, the bonding strength of plywood bonded with UF-OMMT increased by about 97% as compared to that of unmodified UF resin. The positive effects of montmorillonite on water and heat resistance can be attributed to the better barrier properties of the interphase.
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Biodegradable polylactic acid (PLA) has been widely used in fused deposition modeling (FDM) 3D printing. In order to improve its comprehensive properties in 3D printing, in this study, 0-40% content of polybutylene adipate terephthalate(PBAT) was selected to be blended with PLA in a twin-screw extruder; the resulting pellets were drawn into a homogeneous filament; then, PBAT/PLA samples were prepared by FDM 3D printing, and the effects of the dosage of PBAT on the mechanical properties, thermal behavior, surface wettability and melt flowability of the samples were investigated. The results showed that all the samples could be printed smoothly, and the ductility was slightly improved by the increase in the PBAT dosage; the thermal stability of PLA was enhanced by blending with PBAT, and the crystallinity increased monotonically with the increase in PBAT. After blending with PBAT, the surfaces of the samples were more hydrophilic and flowable. The important conclusion achieved in this work was that the PBAT/PLA blends, especially those containing 30%PBAT, showed great potential to replace petroleum-based plastics and are suitable for use in FDM 3D printing technologies for different applications.
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Bamboo, as a potential alternative to biomass materials, has gained more attention from the bamboo manufacturing industry in China. However, the drawbacks, such as the dimensional instability, and low antifungal and hydrophilic properties of bamboo, inhibit its application and shorten its service life. The objective of this work was to analyze the change in chemical components and fungal resistance of moso bamboo with heat treatment. For this objective, moso bamboo specimens were thermally modified in an oven at different temperatures for a fixed duration. The results showed that the parenchymal cells distorted and deformed in comparison to the control after thermal modification. After thermal modification in an oven, the crystallinity index increased from 39% to 53%. Owing to the thermal modification, the hemicellulose and cellulose relative content decreased, as confirmed by FTIR and XPS analysis. Thus, the dimensional stability and antifungal properties of the thermally modified bamboo specimens improved.
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Astragalus is widely cultivated in China, and the residue of Astragalus particles (ARP) can be used as reinforcements in fused filament-fabricated (FFF) natural fiber/Poly(lactic acid)(PLA) biocomposites. To clarify the degradation behavior of such biocomposites, 3D-printed 11 wt% ARP/PLA samples were buried in soil, and the effects of soil burial duration on the physical appearance, weight, flexural properties, morphology, thermal stability, melting, and crystallization properties were investigated. At the same time, 3D-printed PLA was chosen as a reference. The results showed that, with prolonged soil burial, the transparency of PLA decreased (but not obviously), while the surface photographs of ARP/PLA became gray with some black spots and crevices; especially after 60 days, the color of the samples became extremely heterogeneous. After soil burial, the weight, flexural strength, and flexural modulus of the printed samples all reduced, and greater losses happened to ARP/PLA pieces than pure PLA. With an increase in soil burial time, the glass transition, cold crystallization, and melting temperatures, as well as the thermal stability of PLA and ARP/PLA samples, all increased gradually. Additionally, soil burial had a greater effect on the thermal properties of ARP/PLA. The results showed that the degradation behavior of ARP/PLA was more significantly affected by soil burial than the behavior of PLA. Additionally, ARP/PLA more easily degraded in soil than PLA.
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In order to further explore the feasibility of the application of the residue of Chinese herbal medicine in FDM 3D technology and enrich the kinds of printing materials, Astragalus residue powder(ARP)/poly(lactic acid) (PLA) biocomposite was FDM 3D-printed, meanwhile, two traditional biocomposites, i.e., wood flour (WF)/PLA and rice straw powder (RSP)/PLA, were prepared by the same method, and the properties of the biocomposites were comparatively investigated. The results showed that, the tensile and flexural strengths of ARP/PLA were 28.33 MPa and 97.60 MPa, respectively, which were 2.85% and 10.89% smaller than those of WF/PLA, while 15.73% and 7.04% greater than those of RSP/PLA. WF/PLA showed typical brittle fracture characteristics, ARP/PLA and RSP/PLA both showed ductile fracture, but not obviously. Among the three kinds of biocomposites, ARP/PLA was the most thermally stable, followed by WF/PLA and RSP/PLA in turn. The incorporation of natural plant powder had no significant effect on the glassy transition, melting, and cold-crystallization behaviors of PLA, but the crystallinity of PLA could be increased from 0.3% to 2.0% and 1.9%, respectively, by adding ARP and WF. At 20 °C, the storage modulus of ARP/PLA, WF/PLA and RSP/PLA was 2759.4 MPa, 3361.3 MPa, and 2691.5 MPa, respectively, indicating that WF/PLA has the greatest stiffness, and the stiffness of RSP/PLA was the least. In addition to these, all the biocomposites were hydrophilic, the contact angle of the distilled water on the surface of ARP/PLA, WF/PLA or RSP/PLA was correspondingly 73.5°, 77.6° and 71.2°. Overall, it can be concluded that ARP/PLA has moderate strengths, stiffness and wettability, meanwhile, it is the most thermal stable among the three biocomposites, and can be processed at a temperature close to that of PLA. ARP/PLA is suitable as a new kind of feedstock material for FDM 3D printing.
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Poly(lactic acid) (PLA) and Poly(butylene succinate) (PBS) were chosen as raw materials and melt blended by a twin screw extruder and pelletized; then, the pellets were extruded into filaments; after that, various PBS/PLA blending samples were prepared by Fused Deposition Molding (FDM) 3D printing technology using the filaments obtained and the effect of the dosage of PBS on technological properties of 3D-printed specimens was investigated. For comparison, the PLA specimen was also prepared by FDM printing. The tensile strength, tensile modulus, thermal stability, and hydrophilicity became poorer with increasing the dosage of PBS, while the flexural strength, flexural modulus, impact strength, and crystallinity increased first and then decreased. The blend containing 10% PBS (10% PBS/PLA) had the greatest flexural strength of 60.12 MPa, tensile modulus of 2360.04 MPa, impact strength of 89.39 kJ/m2, and crystallinity of 7.4%, which were increased by 54.65%, 61.04%, 14.78%, and 51.02% compared to those of printed PLA, respectively; this blend also absorbed the least water than any other specimen when immersed in water. Different from the transparent PLA filament, 10% PBS/PLA filament presented a milky white appearance. The printed 10% PBS/PLA specimen had a smooth surface, while the surface of the printed PLA was rough. All the results indicated that the printed 10% PBS/PLA specimen had good comprehensive properties, including improved mechanical properties, crystallization performance, and surface quality than PLA, as well as proper wettability and water absorption. The prominent conclusion achieved in this work was that 10% PBS/PLA should be an ideal candidate for biodegradable feedstock among all the PBS/PLA blends for FDM 3D printing.
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Astragalus residue powder (ARP)/thermoplastic starch (TPS)/poly(lactic acid) (PLA) biocomposites were prepared by fused-deposition modeling (FDM) 3D-printing technology for the first time in this paper, and certain physico-mechanical properties and soil-burial-biodegradation behaviors of the biocomposites were investigated. The results showed that after raising the dosage of ARP, the tensile and flexural strengths, the elongation at break and the thermal stability of the sample decreased, while the tensile and flexural moduli increased; after raising the dosage of TPS, the tensile and flexural strengths, the elongation at break and the thermal stability all decreased. Among all of the samples, sample C-which was composed of 11 wt.% ARP, 10 wt.% TPS and 79 wt.% PLA-was the cheapest and also the most easily degraded in water. The soil-degradation-behavior analysis of sample C showed that, after being buried in soil, the surfaces of the samples became grey at first, then darkened, after which the smooth surfaces became rough and certain components were found to detach from the samples. After soil burial for 180 days, there was weight loss of 21.40%, and the flexural strength and modulus, as well as the storage modulus, reduced from 82.1 MPa, 11,922.16 MPa and 2395.3 MPa to 47.6 MPa, 6653.92 MPa and 1476.5 MPa, respectively. Soil burial had little effect on the glass transition, cold crystallization or melting temperatures, while it reduced the crystallinity of the samples. It is concluded that the FDM 3D-printed ARP/TPS/PLA biocomposites are easy to degrade in soil conditions. This study developed a new kind of thoroughly degradable biocomposite for FDM 3D printing.
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22MnB5 hot forming steel is widely used in the automotive industry due to the increasing demand for lightweight vehicles. As surface oxidation and decarburization occur during hot stamping processes, an Al-Si coating is often precoated on surfaces. The coating tends to melt into the melt pool during the laser welding of the matrix and reduce the strength of the welded joint; therefore, it should be removed. The decoating process by sub-nanosecond and picosecond lasers and process parameter optimization were conducted in this paper. The corresponding analysis of the different decoating processes, the mechanical properties and the elemental distribution was carried out after laser welding and heat treatment. It was found that the Al element has an influence on the strength and elongation of the welded joint. The high-power picosecond laser has a better removal effect than the lower power sub-nanosecond laser. The best mechanical properties of the welded joint were obtained under the process conditions of 1064 nm center wavelength, 15 kW power, 100 kHz frequency, and 0.1 m/s speed. In addition, the content of the coating metal elements (mainly Al) melted into the welded joint is reduced with increasing coating removal width, which significantly improves the mechanical properties of the welded joints. Al in the coating rarely melts into the welding pool when the coating removal width is not less than 0.4 mm, and its mechanical properties can meet the automotive stamping requirements for the welded plate.
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Wood flour-poly(butylene succinate)-poly(lactic acid) biocomposite samples were prepared by fused-deposition-molding 3D-printing technology, and modifications with glycerol and a silane coupling agent (KH550) were carried out. The samples were then hydrothermally aged. Modification with glycerol and KH550 enhanced the hydrophilicity of the samples and increased their tensile strength. Hydrothermal aging clearly whitened the surfaces of all the samples and made them more hydrophobic. Meanwhile, their tensile properties and thermal stability became poor; a higher hydrothermal aging temperature affected the mechanical properties more negatively. The modified samples turned out to be more resistant to the hydrothermal aging, and modification with KH550 could improve the anti-hydrothermal aging properties of the samples better than that with glycerol, where the tensile properties and the cross-sectional morphologies of the fractured specimens were concerned. Generally, the effects of hydrothermal aging temperature on the physico-mechanical properties of the printed specimens were greater than those by hydrothermal aging time.
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Grid monitoring is the current development direction of atmospheric monitoring. The micro air quality detector is of great help to the grid monitoring of the atmosphere, so higher requirements are put forward for the accuracy of the micro air quality detector. This paper presents a model to calibrate the measurement data of the micro air quality detector using the monitoring data of the air quality monitoring station. The concentration of six types of air pollutants is the research object of this study to establish a calibration model for the measurement data of the micro air quality detector. The first step is to use correlation analysis to find out the main factors affecting the concentration of the six types of pollutants. The second step uses Ridge Regression (RR) to select variables, find out the factors that have significant effects on the concentration of pollutants, and give the quantitative relationship between these factors and the pollutants. Finally, the predicted value of the ridge regression model and the measurement data of the micro air quality detector are used as input variables, and the Extreme Gradient Boosting (XGBoost) algorithm is used to give the final pollutant concentration prediction model. We named the combined model of ridge regression and XGBoost algorithm RR-XGBoost model. Relative Mean Absolute Percent Error (MAPE), Mean Absolute Error (MAE), goodness of fit (R2), and Root Mean Square Error (RMSE) were used to evaluate the prediction accuracy of the RR-XGBoost model. The results show that the model is superior to some commonly used pollutant prediction methods such as random forest, support vector machine, and multilayer perceptron neural network in the evaluation of various indicators. The model not only has a good prediction effect on the training set but also on the test set, indicating that the model has good generalization ability. Using the RR-XGBoost model to calibrate the data of the micro air quality detector can make up for the shortcomings of the data monitoring accuracy of the micro air quality detector. The model plays an active role in the deployment of micro air quality detectors and grid monitoring of the atmosphere.