Polylactide compositions. The influence of ageing on the structure, thermal and viscoelastic properties of PLA/calcium sulfate composites

High-performance composites prepared by melt-blending polylactide (PLA, l/d isomer ratio of 96/4) with various amounts of β-anhydrite II (AII), the dehydrated form of calcium sulfate hemihydrate obtained by a specific thermal treatment at 500 °C, have been aged to study the evolution of their physical and mechanical properties with time. The effect of 1-year ageing under ambient conditions (below T_g of PLA) for selected composites, i.e., filled with 20 and 40 wt% AII, was determined and compared to unfilled PLA with the same processing and ageing history. Samples with an initial amorphous PLA matrix, obtained by fast quenching from the melt, were characterized before and during ageing. The changes in physical parameters have been studied using dynamic mechanical thermal analysis (DMTA), differential scanning calorimetry (DSC), X-ray diffraction (XRD) and density measurements. Surprisingly, for all the samples, an increase of the storage modulus (E′) was recorded, as a result of ageing. This improvement was ascribed to the reorganization of the PLA structure induced by ageing. The structural reorganization was also reflected by a slight increase of PLA density and changes in thermal behaviour. The X-ray investigations showed unchanged crystallographic structure of AII both during blending with molten PLA and in the composite systems after ageing. The surprising stability of the thermo-mechanical properties of PLA and PLA/AII composites is in agreement with the results of size exclusion chromatography analysis (SEC) which did not show significant changes of PLA molecular weights brought out by ageing.     

Mechanical and thermal properties of green polylactide composites with natural fillers

Green composites of PLA with micropowders derived from agricultural by-products such as oat husks, cocoa shells, and apple solids that remain after pressing have been prepared by melt mixing. The thermal and mechanical properties of the composites, including the effect of matrix crystallization and plasticization with poly(propylene glycol), have been studied. All fillers nucleated PLA crystallization and decreased the cold-crystallization temperature. They also affected the mechanical properties of the compositions, increasing the modulus of elasticity but decreasing the elongation at break and tensile impact strength although with few exceptions. Plasticization of the PLA matrix improved the ductility of the composites.     

Polylactide (PLA)-CaSO4 composites toughened with low molecular weight and polymeric ester-like plasticizers and related performances

Large amounts of stable β-anhydrite II (AII), a specific type of dehydrated gypsum and a by-product of lactic acid production process, can be melt-blended with bio-sourced and biodegradable polylactide (PLA) to produce economically interesting novel composites with high tensile strength and thermal stability.To enhance their toughness, while preserving an optimal stiffness, selected low molecular weight plasticizers (bis(2-ethylhexyl) adipate and glyceryl triacetate) and polymeric adipates with different molecular weights have been mixed with a specific PLA (l/d isomer ratio of 96/4) and 40 wt% of AII using an internal kneader. Addition of up to 10 wt% plasticizer into these highly filled compositions can trigger a fourfold increase of the impact strength with respect to the compositions without any modifier, cold crystallization properties and a significant decrease of their glass transition temperature. Moreover, these ternary compositions (PLA-AII-plasticizer) are clearly characterized by easier processing, notable thermo-mechanical performances and good filler dispersion. This study represents a new approach in formulating novel melt-processable polyester grades with improved characteristic features using PLA as biodegradable polymer matrix.     

New PP/PLA/cellulose composites: effect of cellulose functionalization on accelerated weathering behavior (accelerated weathering behavior of new PP/PLA/cellulose composites)

Polylactic acid (PLA) was used as partial replacement for conventional thermoplastic matrix, new composites comprising cellulose, polypropylene (PP), and PLA being realized. In order to obtain a compatible interface between cellulosic pulp and polymeric matrix, two chemical modifications of cellulose with stearoyl chloride and toluene di‐isocyanate (TDI) were performed, structural changes being evidenced by X‐ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. The composite materials were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, dynamic scanning calorimetry, impact, tensile and melt rheological tests, surface tension, and dynamic vapor sorption. Because promising results for impact strength and Young modulus were recorded when replacing 15% of PP with PLA in blends of PP with the same cellulosic pulp load, the aim of our study was to assess the behavior to accelerate weathering of composites comprising PP, cellulosic pulp, and PLA. Although the slight decrease in the mechanical properties was recorded after accelerated weathering, the use of functionalized cellulose successfully prevented the deterioration of surface materials, especially for composite comprising stearoyl chloride treated cellulose pulp. Copyright © 2015 John Wiley & Sons, Ltd.     

Preparation and properties investigation of PMMA/silica composites derived from silicic acid

Hybrid materials based on silicic acid and polymethyl methacrylate (PMMA) were prepared by in situ bulk polymerization of a silicic acid sol and MMA mixture. Silicic acid sol was obtained by tetrahydrofuran (THF) extraction of silicic acid from water. Silicic acid was prepared by hydrolysis and condensation of sodium silicate in the presence of 3.6 M HCl. As a comparative study, PMMA composites filled by silica particles, which were derived from calcining the silicic acid gel, were prepared by a comparable in situ polymerization. Each set of PMMA/silica composites was subjected to thermal and mechanical studies. Residual THF in PMMA/silicic acid composites impacted the properties of the polymer composites. With increase in silica content, the PMMA composites filled with silica particles showed improved thermal and mechanical properties, whereas a decrease in thermal stability and mechanical strength was found for PMMA composites filled with silicic acid dissolved in THF. With a better compatibility with polymer matrix, silicic acid sol shows better reinforcement than silica particles in PMMA films prepared via blending of the corresponding THF solutions. Copyright © 2008 John Wiley & Sons, Ltd.     

Crosslinking behavior and enhanced mechanical properties of acrylonitrile‐butadiene rubber composites by incorporating aluminum ammonium sulfate particles

The crosslinked structure formed by the metal coordination bonding provides excellent and new properties for rubber materials. Herein, the crosslinking of acrylonitrile‐butadiene rubber (NBR) is induced by introducing aluminum ammonium sulfate (NH₄Al(SO₄)₂·12H₂O) particles. The crosslinking behavior, morphology, mechanical properties, and the Akron abrasion resistance of NBR/NH₄Al(SO₄)₂·12H₂O composites were fully explored. The results show that the three‐dimensional crosslinking structure is held together by metal–ligand coordination bonds between the nitrile group and AI(III). The coordination crosslink density exhibits a considerable increase with the addition of NH₄Al(SO₄)₂·12H₂O. Thus, the mechanical properties and abrasion resistance of the obtained composites are better than that of NBR/sulfur system. Interestingly, the elongation at break for NBR/NH₄Al(SO₄)₂·12H₂O composites is over 2000% due to the nature of coordination bonds. The abrasion volume loss decreases to 0.4 cm³ for NBR/NH₄Al(SO₄)₂·12H₂O composites with 20 phr NH₄Al(SO₄)₂·12H₂O particles as compared to 0.75 cm³ for NBR/sulfur system. The obtained NBR composites with facile preparation and excellent mechanical properties make the composites based on metal coordination bonding attractive for practical use. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 879–886     

The influence of matrix crystallinity,filler grain size and modification on properties of PLA/calcium carbonate composites

Thermal and mechanical properties of polylactide (PLA) composites with different grades of calcium carbonate, 40 nm and 90 nm nanoparticles, and also with submicron particles, unmodified and modified with calcium stearate or stearic acid, obtained by melt mixing, were compared. Films with amorphous and crystalline matrices were prepared and examined.T_g of PLA in the composites remained unaffected whereas its cold crystallization was enhanced by the fillers and predominantly depended on filler content. Filling decreased thermal stability of the materials but their 5% weight loss temperatures well exceeded 250 °C, evidencing stability in the temperature range of PLA processing. The amorphous nanocomposites with modified nanoparticles exhibited improved drawability and toughness without a significant decrease of tensile strength; nearly two-fold increase of the elongation at break and tensile toughness was achieved at 5 wt% content of the modified nanofiller. Lack of surface modification of the filler, larger grain size with an average of 0.9 μm, and matrix crystallinity had a detrimental effect on the drawability. However, the presence of nanofillers and crystallinity improved tensile modulus of the materials by up to 15% compared to neat amorphous PLA.     

Study on mechanical properties and phase morphology of polypropylene/polyolefin elastomer/magnesium hydroxide ternary composites

In this work, elastomer‐toughened polypropylene (PP)/magnesium hydroxide (MH) composites with ethylene–octene copolymer (POE) were prepared in a twin‐screw extruder and then injection‐molded. The structure, mechanical properties, phase morphology, and rheological behaviors of PP/POE/MH ternary composites were studied. The mechanical properties and fracture behaviors of PP/POE/MH ternary composites are strongly influenced by the incorporation of POE copolymer. The addition of POE causes a significant improvement in the impact strength of the composites, from 3.6 kJ/m² in untoughened composites to 47.4 kJ/m² in PP composites containing 30 phr POE. This indicates that POE is very effective in converting brittle PP composites into tough composites. Conversely, the tensile strength and the Young's modulus of the composites decrease with respect to the PP composites, as the weight fraction of POE is increased to 40 phr. Scanning electron microscopy (SEM) study shows a two‐phase morphology where POE, as droplets, is dispersed finely and uniformly in the PP matrix. The rheological behaviors show that the interfacial interaction in the composites is enhanced with increase in POE content. Interparticle interactions give rise to the formation of interparticle network. Copyright © 2009 John Wiley & Sons, Ltd.     

海藻多糖中硫酸基含量对抑制草酸钙晶体形成和修复受损伤肾小管上皮细胞的影响

采用X射线衍射法、傅里叶变换红外光谱仪、扫描电子显微镜、ζ电位仪和电感耦合等离子体发射光谱仪,比较了4种分子量相近(约 3 700 Da)、但硫酸基(—OSO₃^-)含量不同的降解海藻多糖对草酸钙(CaC₂O₄)晶体生长的调控作用;采用细胞实验比较了它们对受损伤肾小管上皮细胞(HK-2)的修复能力。这4种海藻多糖分别是降解紫菜多糖(PY-1)、降解龙须菜多糖(GL-2)、降解羊栖菜多糖(SF-3)和降解裙带菜多糖(UP-4),其—OSO₃^-含量分别为17.9%、13.3%、8.2%和5.5%。结果表明,这4种多糖均能够抑制一水草酸钙(COM)生长,诱导二水草酸钙(COD)生成,增加溶液中可溶性 Ca²⁺离子浓度,增加晶体表面的 ζ 电位绝对值,从而降低晶体的聚集程度;这些多糖均能修复被草酸氧化损伤的HK-2细胞,提高细胞活力和超氧化物歧化酶(SOD)活力,降低丙二醛(MDA)的释放量。结果表明,多糖中—OSO₃^-含量越高,多糖对 CaC₂O₄晶体生长的抑制作用和对受损伤 HK-2细胞的修复作用均越强。     

海藻多糖中硫酸基含量对抑制草酸钙晶体形成和修复受损伤肾小管上皮细胞的影响

采用X射线衍射法、傅里叶变换红外光谱仪、扫描电子显微镜、ζ电位仪和电感耦合等离子体发射光谱仪,比较了4种分子量相近(约3 700 Da)、但硫酸基(—OSO₃^-)含量不同的降解海藻多糖对草酸钙(CaC₂O₄)晶体生长的调控作用;采用细胞实验比较了它们对受损伤肾小管上皮细胞(HK-2)的修复能力。这4种海藻多糖分别是降解紫菜多糖(PY-1)、降解龙须菜多糖(GL-2)、降解羊栖菜多糖(SF-3)和降解裙带菜多糖(UP-4),其—OSO₃^-含量分别为17.9%、13.3%、8.2%和5.5%。结果表明,这4种多糖均能够抑制一水草酸钙(COM)生长,诱导二水草酸钙(COD)生成,增加溶液中可溶性Ca²⁺离子浓度,增加晶体表面的ζ电位绝对值,从而降低晶体的聚集程度;这些多糖均能修复被草酸氧化损伤的HK-2细胞,提高细胞活力和超氧化物歧化酶(SOD)活力,降低丙二醛(MDA)的释放量。结果表明,多糖中—OSO₃^-...     

Mechanical and thermal properties of polylactide/talc microcomposites: before and after accelerated weathering

The purpose of the first part of this study was to investigate effects of micron‐sized talc content on the properties of polylactide (PLA). PLA/talc microcomposites were compounded by melt‐mixing method via twin‐screw extruder, while specimens for testing and analyses were shaped by injection molding. It was observed that, because of the effective stiffening, strengthening, toughening mechanisms of talc, and also their nucleation agent effects for higher crystallinity, many mechanical and thermal properties were improved. In the second part of the study, effects of accelerated weathering on the behavior of PLA microcomposites with 5 wt% talc were investigated by applying ultra violet irradiation and humidity steps according to Cycle‐C of International Organization for Standardization 4892‐3 standards for durations of 100, 200, and 300 hr. Various analyses revealed that, because of the degradation mechanisms of photolysis and hydrolysis during each weathering periods, molecular weight of PLA reduced drastically, that is, mechanical properties almost vanished. Copyright © 2015 John Wiley & Sons, Ltd.     

Flame retardant properties and mechanism of an efficient intumescent flame retardant PLA composites

The charring agent (CNCA‐DA) containing triazine and benzene rings was combined with ammonium polyphosphate (APP) to form intumescent flame retardant (IFR), and it was occupied to modify polylactide (PLA). The flame retardant properties and mechanism of flame retardant PLA composites were investigated by the limited oxygen index (LOI), vertical burning test (UL‐94), thermogravimetric analysis, microscale combustion calorimetry, scanning electron microscopy, laser Raman spectroscopy analysis and X‐ray photoelectron spectroscopy. The analysis from LOI and UL‐94 presented that the IFR was very effective in flame retardancy of PLA. When the weight ratio of APP to CNCA‐DA was 3:1, and the IFR loading was 30%, the IFR showed the best effect, and the LOI value reached 45.6%. It was found that when 20 wt% IFR was loaded, the flame retardancy of PLA/IFR still passed UL‐94 V‐0 rating, and its LOI value reached 32.8%. The microscale combustion calorimetry results showed that PLA/IFR had lower heat release rate, total heat release, and heat release capacity than other composites, and there was an obvious synergistic effect between APP and CNCA‐DA for PLA. IFR containing APP/CNCA‐DA had good thermal stability and char‐forming ability with the char residue 29.3% at 800°C under N₂ atmosphere. Scanning electron microscopy observation further indicated that IFR could promote forming continuous and compact intumescent char layer. The laser Raman spectroscopy analysis and X‐ray photoelectron spectroscopy analysis results indicated that an appropriate graphitization degree of the residue char was formed, and more O and N were remained to form more cross‐linking structure. Copyright © 2016 John Wiley & Sons, Ltd.     

Rheological properties of crystallizing polylactide: Detection of induction time and modeling the evolving structure and properties

Linear viscoelastic properties of polymer melts are highly sensitive to any structural changes, including molecular weight changes and the formation and growth of crystallites. Here, we make use of this sensitivity to study the homogeneous crystallization of polylactide. As this polymer is rather quickly susceptible to thermal degradation even at moderate temperatures, it is essentially impossible to study homogeneous crystallization in the absence of degradation. Thus, the evolution of complex viscosity of a polylactide due to thermal degradation in the absence of crystallization was studied. A simple empirical model is used to characterize the variation of complex viscosity due to thermal degradation and to determine the induction time of homogeneous crystallization at wide range of degrees of supercooling. Next, the evolution of complex viscosity due to crystallization was measured at several temperatures. Based on the results, a phenomenological model describing the viscosity evolution during homogeneous crystallization is proposed and validated. Finally, the linear viscoselastic data in the early stages of crystallization are shown to be consistent with gelation due to the formation of a network of tie molecules between spherulites. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 812–822, 2010     

Relationship between morphology structure and composition of polycaprolactone/Poly(ethylene oxide)/Polylactide copolymeric microspheres

A novel tri‐component copolymer, polycaprolactone/poly(ethylene oxide)/polylactide (PCEL) was synthesized. The effect of the chemical composition on physical properties was investigated by using NMR, differential scanning calorimetry (DSC) and X‐ray diffraction. Both the soft segment poly(ethylene oxide) (PEO) and polycaprolactone (PCL) could enhance the mobility of polymer chains and decrease the crystallizability of the copolymers. The polymeric microspheres, which are of interest for drug delivery systems, were prepared using an emulsification‐solvent evaporation technique. By scanning electron microscopy (SEM) and atomic force microscopy (AFM), the surface morphology of the microspheres was studied. It was found that the presence of PEO segment could improve the hydrophilicity of the copolymers and the morphology of the polymeric microspheres could be altered by adjusting the chemical composition. The accumulation of PEO segments on the outer surface of the polymeric microspheres was proven by X‐ray photoelectron spectroscopy (XPS). It had also been proven that the PCL segment could facilitate the movement of PEO segment to the outer surface. Copyright © 2002 John Wiley & Sons, Ltd.     

纳米碳酸钙微粒填充改性聚丙烯复合材料的力学性能和结晶行为研究

研究了两种不同粒径的纳米碳酸钙(Nano-CaCO3)熔融共混改性均聚聚丙烯(PP)材料的力学性能和结晶行为，结果表明，两种纳米CaCO3填料对PP的B晶形成均有不同程度的诱导作用，并可提高基体结晶温度和结晶速率，从而提高材料的冲击韧性．     

Combined effect of chemically compound graphene oxide‐calcium pimelate on crystallization behavior,morphology and mechanical properties of isotactic polypropylene

The combined nucleation effect of graphene oxide (GO) and calcium pimelate (CaPi) which are chemically compound together (expressed in GO ? CaPi) in isotactic polypropylene (iPP) was investigated. Fourier transform infrared (FTIR), X‐ray diffraction (XRD) and thermogravimetric analysis (TGA) verified that CaPi was chemically compound with GO by chelate bonds. The crystallization behavior and crystalline morphologies of iPP nucleated with different mass ratio of GO and CaPi were investigated. The crystallization peak temperature of iPP nucleated with 0.2 wt% GO ? CaPi with the mass ratio of 1:5 (GO1 ? C5) was increased by 8.3°C when compared with that of pure iPP, and the relative content of β‐crystal reached up to 0.7962. Whereas, the crystallization peak temperature of iPP nucleated with 0.2 wt% GO and CaPi which are blended together by mechanical force (expressed in GO + CaPi) with the mass ratio of 1:5 (GO1 + C5) was only increased by 5.0°C. It was attributed to that the aggregation of GO + CaPi caused the decrease of the crystallization peak temperature, while the GO1 ? C5 uniformly dispersed in the iPP matrix. Unexpectedly, the relative content of β‐crystal of iPP nucleated with 0.02 wt% GO1 ? C5 reached up to 0.8094, and the crystallization peak temperature was increased by 6.7°C compared with that of pure iPP. Meanwhile, the impact strength, tensile strength and heat deflection temperature of iPP nucleated with 0.02 wt% GO1 ? C5 increased by almost 45.86%, 2.03% and 7.7°C, respectively. The iPP nucleated with GO1 ? C5 obtained a balance between stiffness and toughness and the thermo‐mechanical property of nucleated iPP was improved.     

Preparation and properties of gluten/calcium carbonate composites

Environment friendly thermosetting composites were prepared by blending wheat gluten （WG） as matrix, calcium carbonate （CaCO3） as filler and glycerol as plasticizer followed by compression molding the mixture at 120 ℃ to crosslink the WG matrix. Morphology observation showed that the CaCO3 particles were finely dispersed in matrix. Incorporation of CaCO3 up to 10 wt% into the composites caused Young＇s modulus and tensile strength to increase markedly. On the other hand, the moisture absorption and elongation at break decreased slightly.     

加工条件对聚丙烯/尼龙6原位成纤复合材料的影响

分别用不同的加工温度、挤出螺杆转速、牵引速率在单螺杆挤出机中挤出PP／N6（聚丙烯／尼龙6）共混物，得到不同加工条件下的PP／N6原位成纤复合材料．对不同加工条件下得到的共混物的分散相形态、力学性能进行研究．发现螺杆转速越高、牵引速率越快、加工温度越低，分散的N6纤维尺寸越小，复合材料的力学性能越好．     

Fabrication and properties of poly(propylene carbonate)/calcium carbonate composites

Composites of poly(propylene carbonate) (PPC) reinforced with micrometric and nanometric calcium carbonate particles were prepared via melt mixing followed by compression molding. The morphology and mechanical and thermal behaviors of the composites were investigated. Static tensile tests showed that the tensile strength, stiffness, and ductility of the composites tended to increase with increasing contents of micrometric calcium carbonate particles. This improvement in the tensile properties was attributed to good interfacial adhesion between the fillers and matrix, as evidenced by scanning electron microscopy examination. However, because of the agglomeration of calcium carbonate nanoparticles during blending, those composites with nanoparticles exhibited the lowest tensile strength. Thermogravimetric measurements revealed that the incorporation of calcium carbonate into PPC resulted in a slight improvement in its thermooxidative stability. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1806–1813, 2003     

Effects of microscale calcium carbonate and nanoscale calcium carbonate on the fusion,thermal, and mechanical characterizations of rigid poly(vinyl chloride)/calcium carbonate composites

A Haake torque rheometer equipped with an internal mixer has been used to study the influence of microscale calcium carbonate (micro‐CaCO₃) and nanoscale calcium carbonate (nano‐CaCO₃) on the fusion, thermal, and mechanical characteristics of rigid poly(vinyl chloride) (PVC)/micro‐CaCO₃ and PVC/nano‐CaCO₃ composites, respectively. The fusion characteristics discussed in this article include the fusion time, fusion temperature, fusion torque, and fusion percolation threshold (FPT). The fusion time, fusion temperature, and FPT of rigid PVC/calcium carbonate (CaCO₃) composites increase with an increase in the addition of micro‐CaCO₃ or nano‐CaCO₃. In contrast, the fusion torque of rigid PVC/CaCO₃ composites decreases with an increase in the addition of micro‐CaCO₃ or nano‐CaCO₃. The results of thermal analysis show that the first thermal degradation onset temperature (T_onset) of rigid PVC/micro‐CaCO₃ is 7.5 °C lower than that of PVC. Meanwhile, the glass‐transition temperature (T_g) of rigid PVC/micro‐CaCO₃ is similar to that of PVC. However, T_onset and T_g of PVC/nano‐CaCO₃ composites can be increased by up to 30 and 4.4%, respectively, via blending with 10 phr nano‐CaCO₃. Mechanical testing results for PVC/micro‐CaCO₃ composites with the addition of 5–15 phr micro‐CaCO₃ and PVC/nano‐CaCO₃ composites with the addition of 5–20 phr nano‐CaCO₃ are better than those of PVC. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 451–460, 2006