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1.
Poly(lactic acid)(PLA) composites with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO) and DOPOcontaining polyhedral oligomeric silsesquioxane(DOPO-POSS) were prepared via melting extrusion and injection molding. The crystallization, mechanical, and flame-retardant properties of PLA/DOPO and PLA/DOPO-POSS were investigated by differential scanning calorimetry(DSC), X-ray diffraction(XRD), tensile testing, thermogravimetric analysis(TGA), limiting oxygen index(LOI),and cone calorimeter test. The DSC results showed that the DOPO added could act as a plasticizer as reflected by lower glass transition temperature and inhibited crystallization of part of the PLA; the DOPO-POSS acted like a filler in the PLA matrix and slightly improved the crystallinity of the PLA matrix. The XRD and DSC analyses indicated that the PLA composites by cold molding injection were amorphous, and the PLA composites following a heat treatment in an oven at 120 °C for 30 min achieved crystallinity. All the PLA and its composites after heat treatment had improved mechanical properties. The thermogravimetric analysis(TGA) tests showed that the PLA,DOPO and DOPO-POSS decomposed separately in the PLA/DOPO and PLA/DOPO-POSS, respectively. The cone calorimeter tests offered clear evidence that addition of the DOPO-POSS resulted in an evident reduction of 25% for the peak of heat release rate(p-HRR).It was also confirmed that the crystalline flame-retardant PLA composites after heat treatment had better flame retardant properties than the amorphous PLA composites prepared by the cold molding.  相似文献   

2.
The present study proposed a series of sustainable polyamide/cellulose composites with up to 60% bio-based content to address environmental issues arising from using fossil-based polymers. Furthermore, it addressed one of the most challenging cellulose/polymer composites' issues, filler/matrix compatibility. Accordingly, the microcrystalline cellulose (MCC) surface was treated through the grafting of n-octadecyl isocyanate (ODI) molecules. The elemental analysis confirmed the substitution of approximately 9 ODI molecules per 100 anhydroglucose units, resulting in superhydrophobic MCC formation with a water contact angle of 130°. The surface-modified MCC was melt blended with a bio-based low–melting point polyamide, developed through copolymerization of 11-aminoundecanoic acid and 12-aminolauric acid. Scanning electron microscopy images confirmed no evidence of surface-modified MCC agglomeration, even at a high loading of 30 wt%, suggesting a uniform dispersion of the filler particles and excellent compatibility between two phases. Consequently, the storage modulus, tensile modulus, and yield stress were enhanced by 40%, 100%, and 50%, respectively, in the composite sample with 30 wt% of MCC, proving excellent stress transformation from the matrix to particles arose from good adhesion between cellulose particles and polyamide chains. Furthermore, all samples revealed suitable melt flowability and viscoelastic performances, suggesting their excellent processability, a critical property for engineered thermoplastics. On top of that, the presence of the surface-modified particles considerably decreased water uptake capacity and water vapor transmission of the polymer matrix, making it interesting for specific applications like packaging films.  相似文献   

3.

Rigid polyurethane foam/aluminum diethylphosphinate (RUPF/ADP) composites were prepared by one-step water-blown method. Furthermore, scanning electron microscope (SEM), thermal conductivity meter, thermogravimetric analysis (TGA), limiting oxygen index, Underwriters Laboratories vertical burning test (UL-94) and microsacle combustion calorimetry were applied to investigate thermal conductivity, thermal stability, flame retardancy and combustion behavior of RPUF/ADP composites. Thermogravimetric analysis–Fourier transform infrared spectroscopy (TG–FTIR) was introduced to investigate gaseous products in degradation process of RPUF/ADP composites, while SEM and X-ray photoelectron spectroscopy were used to research char residue of the composites. It was confirmed that RPUF/ADP composites presented well cell structure with density of 53.1–59.0 kg m?3 and thermal conductivity of 0.0425–0.0468 W m?1 K?1, indicating excellent insulation performance of the composites. Flame retardant test showed that ADP significantly enhanced flame retardancy of RPUF/ADP composites, RPUF/ADP30 passed UL-94 V-1 rating with LOI of 23.0 vol%. MCC test showed that ADP could significantly decrease peak of heat release rate (PHPR) of RPUF/ADP composites. PHPR value of RPUF/ADP20 was decreased to 158 W g?1, which was 21.8% reduced compared with that of pure RPUF. TG–FTIR test revealed that the addition of ADP promoted the release of CO2, hydrocarbons and isocyanate compound in first-step degradation of RPUF matrix while inhibited the release of CO in second step degradation. Char residue analysis showed that the addition of ADP promoted polyurethane molecular chain to form aromatic and aromatic heterocyclic structure, enhancing strength and compactness of the char. This work associated a gas–solid flame retardancy mechanism with the incorporation of ADP, which presented an effective strategy for preparation of flame retardant RPUF composites.

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4.
Polylactic acid (PLA) nanocomposites were prepared using cellulose nanowhiskers (CNW) as a reinforcing element in order to asses the value of this filler to reduce the gas and vapour permeability of the biopolyester matrix. The nanocomposites were prepared by incorporating 1, 2, 3 and 5 wt% of the CNW into the PLA matrix by a chloroform solution casting method. The morphology, thermal and mechanical behaviour and permeability of the films were investigated. The CNW prepared by acid hydrolysis of highly purified alpha cellulose microfibers, resulted in nanofibers of 60–160 nm in length and of 10–20 nm in thickness. The results indicated that the nanofiller was well dispersed in the PLA matrix, did not impair the thermal stability of this but induced the formation of some crystallinity, most likely transcrystallinity. CNW prepared by freeze drying exhibited in the nanocomposites better morphology and properties than their solvent exchanged counterparts. Interestingly, the water permeability of nanocomposites of PLA decreased with the addition of CNW prepared by freeze drying by up to 82% and the oxygen permeability by up to 90%. Optimum barrier enhancement was found for composites containing loadings of CNW below 3 wt%. Typical modelling of barrier and mechanical properties failed to describe the behaviour of the composites and appropriate discussion regarding this aspect was also carried out. From the results, CNW exhibit novel significant potential in coatings, membranes and food agrobased packaging applications.  相似文献   

5.
Ethylene vinyl acetate (EVA) composites filled with zeolite (25 vol.%) were prepared using an internal mixer followed by compression molding machine. In order to enhance the thermal properties and fire retardancy of the composites, an intumescent flame retardant consisting of ammonium polyphosphate (APP)/pentaerythritol (PER) was incorporated into the composites. Two kinds of flame retardants were used which are untreated APP (APP1) and silane treated APP (APP2), where their effectiveness was evaluated by means of differential scanning calorimetry (DSC) and also thermogravimetric analysis (TGA). The results showed that both types of flame retardants have the ability to enhance the thermal stability of EVA/zeolite composites by producing charred layer which protects the underlying composites from the action of flame. Moreover, the incorporation of APP1 and APP2 has a significant effect on the composites degree of crystallinity. Meanwhile the results of tensile testing showed that the composites with APP2/PER exhibit better tensile properties compared to that with APP1/PER. This is expected since the application of silane-treated APP (APP2) could improve the dispersion of APP particles within EVA matrix.  相似文献   

6.
On the determination of crystallinity and cellulose content in plant fibres   总被引:2,自引:0,他引:2  
A comparative study of cellulose crystallinity based on the sample crystallinity and the cellulose content in plant fibres was performed for samples of different origin. Strong acid hydrolysis was found superior to agricultural fibre analysis and comprehensive plant fibre analysis for a consistent determination of the cellulose content. Crystallinity determinations were based on X-ray powder diffraction methods using side-loaded samples in reflection (Bragg-Brentano) mode. Rietveld refinements based on the recently published crystal structure of cellulose Iβ followed by integration of the crystalline and amorphous (background) parts were performed. This was shown to be straightforward to use and in many ways advantageous to traditional crystallinity determinations using the Segal or the Ruland–Vonk methods. The determined cellulose crystallinities were 90–100 g/100 g cellulose in plant-based fibres and 60–70 g/100 g cellulose in wood based fibres. These findings are significant in relation to strong fibre composites and bio-ethanol production.  相似文献   

7.

The objective of this work is the use of cellulose fibers extracted from coir fibers as Janus nanocylinders to suppress the phase retraction and coalescence in poly(lactic) acid/polypropylene bio-blend polymers via prompting the selective localization of cellulose fibers at the interface using chemical modification. The untreated and modified cellulose fibers extracted from coir fibers using a silane molecule (tetraethoxysilane) were used as reinforcement and as Janus nanocylinder at two weight contents (2.5 wt% and 5 wt%) to manipulate the morphology of the bio-blends. Their bio-composites with PLA-PP matrix were prepared via melt compounding (at PLA/PP: 50/50). The treatment effect on component interaction and the bio-composites properties have been studied via Scanning electron microscopy, infrared spectroscopy, and differential calorimetry analysis. The mechanical and rheological properties of nanocomposites were similarly assessed. Young's modulus and tensile strength of PLA-PP nanocomposites reinforced by silanized cellulose fibers show a great enhancement as compared to a neat matrix. In particular, there was a gain of 18.5% in Young's modulus and 11.21% in tensile strength for silanized cellulose fiber-based bio-blend composites at 5 wt%. From the rheological point of view, it was found that the silanized cellulose fibers in PLA-PP at both fibers loading enhances the adhesion between both polymers leading to tuning their morphology from sea-island to the continuous structures with the appearance of PLA microfibrillar inside of bio-composites. This change was reflected in the relaxation of the chain mobility of the bio-blend composites.

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8.
The isothermal and non-isothermal decompositions of cellulose nanofiber (CNF) and microfibrillated cellulose (MFC)-filled polypropylene (PP) composites were evaluated and compared with microcrystalline cellulose (MCC)-filled composites by means of thermogravimetric analysis (TG). X-ray diffraction was employed to evaluate crystallinity of the composites. The degree of maximum thermal degradation (ultimate DTG peak value) increased and thermal degradation onset temperature decreased as the cellulose content increased because the thermal stability of cellulose fillers is lower than that of neat PP, but the thermal degradation of the composite was hindered at higher temperature conditions because of the increased residual mass content of the cellulose nanofibril fillers compared to the matrix polymer. The isothermal residual mass of the cellulose nanofibril-filled PP composites under melt blending and injection molding temperatures was decreased marginally by incorporation of the cellulose reinforcement but still exhibited considerable isothermal stability. The raw materials and composites examined in this study were not affected by the manufacturing process temperatures utilized to produce the composites. The MCC decreased the composite crystallinity while the nano-sized cellulose (CNF and MFC) did not appear to have an effect on crystallinity.  相似文献   

9.
蒲俊文 《高分子科学》2014,32(10):1363-1372
in order to improve the optical and mechanical performances of waterborne polyurethane (WPU), nanocrystalline cellulose (NCC)/WPU composites were synthesized in this study. NCC (prepared by acid hydrolysis of cotton fiber) was modified by (3-aminopropyl)triethoxysilane (APTES) to enhance its compatibility with WPU, and the surface-modified NCC was characterized by grafting ratio, crystallinity and contact angle (CA). NCC/WPU composites were examined by scanning electron microscopy (SEM), X-ray powder diffraction (XRD) and thermogravimetric analysis (TG). The anti-yellowing property, specular gloss, pencil hardness, and abrasion resistance of NCC/WPU composites were investigated by the methods of Chinese National Standards GB/T 23999-2009, GB/T 9754-2007, GB/T 6739-2006 and GB/T 1768-2006, respectively. The results showed that the grafting ratio of NCC modified by 6% APTES was 36.01% and the crystallinity of modified NCC was decreased with the enhancement of APTES. CA of the modified NCC was decreased by 28.8% and the nanoparticles were homogeneously dispersed in the WPU matrix. The XRD patterns of the NCC/WPU composites were relatively steady, while the thermal stability of the composites was enhanced by 6.7% with 1.0 wt% modified NCC. Modified NCC affected the specular gloss of NCC/WPU composites more obviously than the anti-yellowing property. The pencil hardness of NCC/WPU composites was increased from 2H to 4H by addition of NCC and the abrasion resistance of the composites was enhanced significantly. In general, NCC/WPU composites showed significant improvements in the optical and mechanical performances.  相似文献   

10.
The structure of film composites based on methyl cellulose and fillers, such as montmorillonite and silver nanoparticles stabilized by poly(vinylpyrrolidone) (Poviargol), is studied by X-ray diffraction. In the composite, montmorillonite nanoparticles exist in the exfoliated state; when the content of the nanoparticles is below 7 wt %, the crystallinity of methyl cellulose increases. Owing to the presence of the filler and structural ordering of the matrix, elastic characteristics improve and the degradation temperature of the composites increases. The X-ray structural data show that the Ag particles in the methyl cellulose-Poviargol composite are 30 nm in size. The introduction of up to 20 wt % Poviargol assists the crystallization of methyl cellulose. The strength and strain characteristics of the film composites based on methyl cellulose and Poviargol make it possible to use these composites in medicine and agriculture.  相似文献   

11.
Regenerated cellulose blend film with thermoplastic polyurethane (TPU) was successfully prepared by coagulating cellulose/TPU solution with water in the presence of a thermoplastic polyurethane elastomer (TPU). Compared with pristine regenerated cellulose film, the toughness and thermal stability of the blend film was significantly improved. For example, the elongation at break was increased from 11% of pristine cellulose film to 51% of blend film with 20 wt. % TPU. The 50% weight loss temperature of this blend film was increased by 33 °C compared to neat cellulose. The relaxation transition temperature of cellulose was decreased with the addition of TPU through dynamic mechanical thermal analysis. The oxygen permeability was decreased from 2.3 × 10−10 cm3 cm/cm2 s Pa of pristine cellulose film to 0.08 × 10−10 cm3 cm/cm2 s Pa of the blend film with 20 wt.%. TPU The X-ray diffraction spectra showed that the crystallinity of cellulose decreased with incorporation of TPU. The images of scanning electron microscope discovered that there was good compatibility between cellulose and TPU. TPU was nano-dispersed in cellulose matrix. The blend film still maintained quite good transparency.  相似文献   

12.
Biodegradable PLA composites were prepared using microcrystalline cellulose (MCC) and silver (Ag) nanoparticles. The main objective of the present study is to develop new biopolymer composites with good mechanical properties, thermal stability, maintaining the optical transparency and also providing antimicrobial properties through silver nanoparticle introduction. Composites were prepared with 1%wt of Ag nanoparticles and 5%wt of MCC using a twin-screw microextruder; film parameters were optimized in order to obtain a thickness range between 20 and 60 μm.PLA composites maintained optical transparency properties of the matrix, while MCC was able to reduce polymer permeability. Thermal analysis revealed that MCC increased PLA crystallinity and the mechanical properties of the composites demonstrated that tensile modulus was improved by microcrystalline cellulose.  相似文献   

13.
A novel flame retardant containing cellulose, phosphorus and ferrum complex (Cell‐P‐Fe) was successfully synthesized and then it was used as flame retardants in epoxy resins (EP). Due to the present of acid sources and carbon sources, the Cell‐P‐Fe exhibits improved thermal stability and flame retardant properties. The EP/Cell‐P‐Fe composites with 10 wt% of Cell‐P‐Fe show remarkably improved LOI and UL‐94 values compared with the flame retardants without ferrum. At the loading of 10.0 wt% flame retardants, the char yield for EP/Cell‐P‐Fe composites increased to 29.1 wt%, indicating the improved thermal stability at high temperature. Moreover, thermogravimetric analysis, morphology of char residues and FTIR results demonstrate that stable char layers are formed on the surface of the composites during the combustion, attributing to the catalytic carbonization effect of Fe and phosphorus and the present of cellulose as carbon source. The stable char layers, which can protect the underlying materials from heat and oxygen, play an important role in the flame retardancy enhancement.  相似文献   

14.
《先进技术聚合物》2018,29(3):1068-1077
The effect of 1,3,5‐triglycidyl isocyanurate (TGIC) as a synergistic agent on the fire retardancy, thermal, and mechanical properties for polyamide 6/aluminium diethylphosphinate (PA6/AlPi) composites were investigated in detail by limiting oxygen index; vertical burning (UL‐94); cone calorimeter; thermal gravimetric analysis; rheological measurements; and the tests of tensile, flexural, and Izod impact strength. The morphologies and chemical compositions of the char residue were investigated by scanning electron microscopy, X‐ray photoelectron spectroscopy, and Fourier transform infrared spectra. The results demonstrated that AlPi and TGIC exerted an evident synergistic effect for flame retardant PA6 matrix, and the PA6/AlPi/TGIC composites with the thickness of 1.6 mm successfully passed UL‐94 V‐0 rating with the limiting oxygen index value of 30.8% when the total loading amount of AlPi/TGIC with the mass fraction of 97:3 was 11 wt%. However, the samples failed to pass the UL‐94 vertical burning tests when AlPi alone is used to flame retardant PA6 matrix with the same loading amount. The thermal gravimetric analysis data revealed that the introduction of TGIC promoted the char residue formation at high temperature. The rheological measurement demonstrated that the incorporation of TGIC improved the storage modulus, loss modulus, and complex viscosity of PA6/AlPi/TGIC composites comparing with that of neat PA6 and PA6/AlPi composites due to the coupling reaction between TGIC and the terminal groups of PA6 matrix. The morphological structures of char residues demonstrated that TGIC benefited to the formation of more homogenous and integrated char layer with no defects and holes on the surface comparing with that of PA6/AlPi composites during combustion. The higher melt viscosity of composites and the integrated and sealed char layer effectively inhibited the volatilization of flammable gas into the combustion zone and then led to the reduction of the heat release. The results of mechanical properties revealed that the incorporation of TGIC enhanced the mechanical properties for PA6/AlPi/TGIC composites comparing with that of PA6/AlPi composites with the same loading amount of flame retardant caused by the chain extension effect of TGIC. As a result, the flame retardancy and mechanical properties of PA6/AlPi composites simultaneously enhanced due to the introduction of TGIC.  相似文献   

15.
《先进技术聚合物》2018,29(2):860-866
The exploration of green flame retardants is of great significance for fire safety, ecological environment protection, and resource saving. Herein, a novel phosphorus containing chitosan‐cobalt complex (CS‐P‐Co) was successfully synthesized for the first time and then introduced into polylactic acid matrix. Owning to the formation of cobalt salts, the CS‐P‐Co exhibits good thermal stability and catalytic char effect. The as‐fabricated biodegradable polylactic acid/CS‐P‐Co composites with small amounts of CS‐P‐Co (≤ 4.0 wt%) show remarkably improved flame retardancy, such as decreased peak heat release rate and total heat release by 23.0% and 20.0%, respectively. Scanning electron microscopy, Thermogravimetric analysis, and Raman results demonstrate that compact graphitized char layers are formed on the composite surface during combustion, attributed to the catalytic effect of CS‐P‐Co. The char inhibits diffusion of heat, mass, and oxygen, which plays a key role in the flame retardancy enhancement.  相似文献   

16.
Aluminum salts of phosphinic acid mixture of diisobutylphosphinic acid and monoisobutylphosphinic acid (HPA-2TBA-Al) and glass fibres were compounded with polyamide 6 to prepare a series of flame retardant GF/PA6 composites via melt blending. The flame retardance and burning behaviors of the composites were investigated by limiting oxygen index (LOI), vertical burning test (UL-94), and Cone calorimeter test. The thermal properties and decomposition kinetics were investigated by thermogravimetric analysis (TGA) under N2 atmosphere. Addition of HPA-2TBA-Al results in an increased LOI value, a UL-94 V-0 rating together with a decrease in both the values of PHRR and THR in Cone calorimetric analysis. Visual observations and scanning electronic microscopy (SEM) after flame retardant tests confirmed the char-formation which acts as a fire barrier in condense phase. Analysis of cone calorimeter data indicates that gas phase flame retardant mechanism exists in the GFPA6/HPA-2TBA-Al system.  相似文献   

17.
Environmentally-friendly SPI/cellulose whisker composites were successfully prepared using a colloidal suspension of cellulose whiskers, to reinforce soy protein isolate (SPI) plastics. The cellulose whiskers, having an average length of 1.2 microm and diameter of 90 nm, respectively, were prepared from cotton linter pulp by hydrolyzing with sulfuric acid aqueous solution. The effects of the whisker content on the morphology and properties of the glycerol-plasticized SPI composites were investigated by scanning electron microscopy, dynamic mechanical thermal analysis, differential scanning calorimetry, ultraviolet-visible spectroscopy, water-resistivity testing and tensile testing. The results indicated that, with the addition of 0 to 30 wt.-% of cellulose whiskers, strong interactions occurred both between the whiskers and between the filler and the SPI matrix, reinforcing the composites and preserving their biodegradability. Both the tensile strength and Young's modulus of the SPI/cellulose whisker composites increased from 5.8 to 8.1 MPa and from 44.7 to 133.2 MPa, respectively, at a relative humidity of 43%, following an increase of the whisker content from 0 to 30 wt.-%. Furthermore, the incorporation of the cellulose whiskers into the SPI matrix led to an improvement in the water resistance for the SPI-based composites.  相似文献   

18.
In order to investigate the effect of simulated acid rain (SAR) corrosion on the wear-resistance properties of straw fiber/polyvinyl chloride (SPVC) composites, four types of straw fibers (wheat straw (WS), rice straw (RS), corn straw (CS), and sorghum straw (SS) fibers) were utilized and incorporated into poly(vinyl chloride) (PVC). The results show that the SS fibers have high levels of cellulose, lignin and crystallinity, and it also exhibited high adhesion strength with PVC matrix, which endow the SS/PVC with high wear-resistance compared with other three SPVC composites. After SAR corrosion, SPVC composites exhibited severe degradation of the physical, mechanical, and thermal properties, and the fibers were easily pulled out from the matrix to form abrasive particles. The high-speed fiber debris in high-temperature and high-loading environments can be deemed a kind of “incompressible lumps” that will form a certain abrasive wear.  相似文献   

19.
Composites of cellulose acetate and polysiloxane were prepared using 3-isocyanatepropyltriethoxysilane, as a coupling agent. The structure, the thermal and dynamic-mechanical behaviors, and the morphology of the obtained composites were investigated. The composites showed phase separation which was confirmed by the presence of siloxane micro- and nano-domains dispersed in the cellulose acetate matrix, with good interfacial adhesion between the phases. The results demonstrated that the incorporation of a polysiloxane phase on a cellulose acetate matrix caused a decrease in the glass transition temperature, storage modulus and hardness. The proposed methodology was seen to be convenient for the preparation of cellulose acetate/polysiloxane composites with useful properties.  相似文献   

20.
The flame‐retardant polylactic acid (PLA) has been prepared via mixing the flame retardant TGIC‐DOPO derived from phosphaphenanthrene and triazine groups into matrix. The flame retardancy of TGIC‐DOPO/PLA composites was characterized using the limiting oxygen index (LOI), vertical burning test (UL94), and cone calorimeter test. Results reveal that the 10%TGIC‐DOPO/PLA composite obtained 26.1% of LOI and passed UL94 V‐0 rating. The flame‐retardant mechanism of PLA composites was characterized via thermogravimetric analysis (TGA), pyrolysis gas chromatography/mass spectroscopy, and TGA‐Fourier transform infrared. It discloses that TGIC‐DOPO promoted PLA decomposing and dripping early, and it also released the fragments with quenching and dilution effects. These actions of TGIC‐DOPO contribute to reducing the burning intensity and extinguishing the fire on droplets, thus imposing better flame retardancy to PLA. When TGIC‐DOPO was partly replaced by melamine cyanuric with dilution effect and hexa‐phenoxy‐cyclotriphosphazene with quenching effect in composites respectively, the results confirm that TGIC‐DOPO utilize well‐combination in dilution effect and quenching effect to flame retard PLA. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

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