Poly(L‐lactic acid) nanocomposites with layered double hydroxides functionalized with ibuprofen

The detrimental effect of cell adhesion on polymer surfaces has been a limiting factor in the medical deployment of many implants. We examined the potential to decrease cell proliferation while simultaneously increasing mechanical performance through Zn–Al layered double hydroxide (LDH) organically modified with ibuprofen dispersed in poly(L ‐lactic acid) (PLLA). These composites are commonly referred to as nanocomposites. The thermophysical and mechanical properties of the hybrids were studied with wide‐angle X‐ray diffraction (WAXD), transmission electron microscopy (TEM), differential scanning calorimetry, thermogravimetric analysis, dynamic mechanical analysis, and tensile testing. The WAXD and TEM results indicated that intercalated and exfoliated nanocomposites were obtained. The storage modulus, tensile modulus, and ultimate tensile strength were improved. The LDH affected the cold crystallization and reduced the thermal stability of the neat PLLA. Smooth muscle cells were used for in vitro studies of the nanocomposites. It was found that the hybrids reduced cell proliferation, and the amount of cell reduction was related to ibuprofen release. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Properties of Poly(3‐hydroxybutyric acid) Composites with Flax Fibres Modified by Plasticiser Absorption

Natural fibre‐biopolymer composites have been prepared from flax and polyhydroxybutyrate (PHB). The flax was modified by drying, followed by plasticiser absorption to replace the water lost to prevent embrittlement. This protects the fibres from problems associated with their water content and changes in water content due to equilibration with the environment. Flax and PHB showed good interfacial adhesion, which was decreased when plasticisers were present. Some plasticiser migrated from the flax to PHB and caused complex changes in the glass transition, crystallisation and crystallinity of the PHB. Morphology of the composites was examined by scanning electron microscopy (SEM) and optical microscopy (OM), SEM provided information on the interfacial adhesion through fractography. OM showed extensive transcrystallinity along the fibre surfaces. Dynamic mechanical analysis was used to measure elastic and damping characteristics and their relation to composition and morphology.

SEM micrograph of the PHB‐plasticiser‐flax system PHB‐PEG‐flax.     

Mechanical and thermal properties of starch‐filled poly(D,L‐lactic acid)/poly(hydroxy ester ether) biodegradable blends

The mechanical, structural, and thermal properties of injection‐molded composites of granular cornstarch, poly(D ,L ‐lactic acid) (PDLLA), and poly(hydroxy ester ether) (PHEE) were investigated. These composites had high tensile strengths, ranging from 17 to 66 MPa, at starch loadings of 0–70 wt %. Scanning electron microscopy micrographs of fracture specimens revealed good adhesion between the starch granule and the polymer matrix, as evidenced by broken starch granules. The adhesion of the starch granules to the polymer matrix was the greatest when the matrix PDLLA/PHEE ratios ranged from zero to unity. At a PDLLA/PHEE ratio of less than unity, as the starch content increased in the composites, there was an increase in the tensile strength and modulus, with a concurrent decrease in elongation. The effects of starch on the mechanical properties of starch/PDLLA composites showed that as the starch content of the composite increased, the tensile strength and elongation to break decreased, whereas Young's modulus increased. In contrast, the tensile strength of starch/PHEE composites increased with increasing starch content. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1775–1786, 2003     

Mechanical and Morphological Studies of Poly(propylene)‐Filled Eggshell Composites

Poly(propylene) (PP) composites were prepared by using eggshell (ES) as filler and their mechanical properties were compared with those using talc (TA) and calcium carbonate (CC) of different grain sizes (X₅₀). A decrease in impact strength and deformation at break with increase in filler content was observed. The PP composite with ES (X₅₀ = 8.4 µm) was stiffer than those with CC (X₅₀ = 0.7 µm). The hybrid composite PP‐ES‐TA showed a similar stiffness as the PP‐TA composites due to the similar morphology of TA (X₅₀ = 0.5 µm) and ES, when TA was replaced up to 75 wt.‐% by ES. SEM study revealed evidence of improved interfacial bonding between PP and ES in theirs composites.

     

Fracture Toughness of Graded Metal-Particulate/Brittle-Matrix Composites

A series of 0, 10, and 25 vol% metal-particulate/glass-matrix composites were prepared, with the composite volume fraction both constant and graded across the specimen bulk. Applied-moment double-cantilever-beam (AMDCB) fracture toughness results show, in general, that the graded composites had equivalent values when compared with the constant fraction specimens. This equivalence in toughness occurred despite lower overall volume fraction particulate phase and composite density for the graded composites. Additionally, these results indicate the necessity of a minimum composite layer thicknes for optimization of toughening.     

Statistical Optimization of Ternary Blends of Poly(lactic acid)/Ethylene Acrylate Copolymer/Wood Flour Composites

Factorial design analyses and numerical optimization are performed to establish material compositions (wood flour content, particle size, and impact modifier content) and mechanical property relationships for PLA/wood flour composites. Numerical optimization produces two scenarios based on materials compositions to manufacture composites with similar mechanical properties as unfilled PLA. High wood flour and impact modifier contents are required for composites made with fine wood flour particles, whereas the formulation requires low wood flour content and excludes impact modifiers for composites with coarse wood flour particles. These optimization solutions are validated experimentally.

     

Biodegradable composites of poly(butylene succinate‐co‐butylene adipate) reinforced by poly(lactic acid) fibers

Biodegradable composites of poly(butylene succinate‐co‐butylene adipate) (PBSA) reinforced by poly(lactic acid) (PLA) fibers were developed by hot compression and characterized by Scanning electron microscopy (SEM), differential scanning calorimetry (DSC), dynamic mechanical analyzer, and tensile testing. The results show that PBSA and PLA are immiscible, but their interface can be improved by processing conditions. In particular, their interface and the resulting mechanical properties strongly depend on processing temperature. When the temperature is below 120 °C, the bound between PBSA and PLA fiber is weak, which results in lower tensile modulus and strength. When the processing temperature is higher (greater than 160 °C), the relaxation of polymer chain destroyed the molecular orientation microstructure of the PLA fiber, which results in weakening mechanical properties of the fiber then weakening reinforcement function. Both tensile modulus and strength of the composites increased significantly, in particular for the materials reinforced by long fiber. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43530.     

Enzymatic Degradation of Biodegradable Polyester Composites of Poly(L‐lactic acid) and Poly(ε‐caprolactone)

Summary: Two different types of biodegradable polyester composites, PLLA fiber‐reinforced PCL and PCL/PLLA blend films were prepared at PCL/PLLA ratio of 88/12 (w/w), together with pure PCL and PLLA films. Their enzymatic degradation was investigated by the use of Rhizopus arrhizus lipase and proteinase K as degradation enzymes for PCL and PLLA chains, respectively. In the FRP film, the presence of PLLA fibers accelerated the lipase‐catalyzed enzymatic degradation of PCL matrix compared with that in the pure PCL film, whereas in the blend film, the presence of PLLA chains dissolved in the continuous PCL‐rich domain retarded the lipase‐catalyzed enzymatic degradation of PCL chains. In contrast, in the FRP film, the proteinase K‐catalyzed enzymatic degradation of PLLA fibers was disturbed compared with that of the pure PLLA film, whereas in the blend film, the proteinase K‐catalyzed enzymatic degradation rate of particulate PLLA‐rich domains was higher than that of pure PLLA film. The reasons for aforementioned enhanced and disturbed enzymatic degradation are discussed.

Normalized PCL weight loss of pure PCL, FRP, and blend films as a function of Rhizopus arrhizus lipase‐catalyzed enzymatic degradation time.     

Poly(lactic acid)-based biocomposites reinforced with kenaf fibers

Biodegradable thermoplastic-based composites reinforced with kenaf fibers were prepared and characterized. Poly(lactic acid) (PLA) was selected as polymeric matrix. To improve PLA/fibers adhesion, low amount of a proper reactive coupling agent, obtained by grafting maleic anhydride onto PLA, was added during matrix/fibers melt mixing. Compared with uncompatibilized composites, this compatibilization strategy induces a strong interfacial adhesion and a pronounced improvement of the mechanical properties. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermal and mechanical properties of plasticized poly(L‐lactic acid)

Acetyl tri‐n‐butyl citrate (ATBC) and poly(ethyleneglycol)s (PEGs) with different molecular weights (from 400 to 10000) were used in this study to plasticize poly(L‐lactic acid) (PLA). The thermal and mechanical properties of the plasticized polymer are reported. Both ATBC and PEG are effective in lowering the glass transition (T_g) of PLA up to a given concentration, where the plasticizer reaches its solubility limit in the polymer (50 wt % in the case of ATBC; 15–30 wt %, depending on molecular weight, in the case of PEG). The range of applicability of PEGs as PLA plasticizers is given in terms of PEG molecular weight and concentration. The mechanical properties of plasticized PLA change with increasing plasticizer concentration. In all PLA/plasticizer systems investigated, when the blend T_g approaches room temperature, a stepwise change in the mechanical properties of the system is observed. The elongation at break drastically increases, whereas tensile strength and modulus decrease. This behavior occurs at a plasticizer concentration that depends on the T_g‐depressing efficiency of the plasticizer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1731–1738, 2003     

Morphology,Thermal and Mechanical Properties of Poly(propylene) Fibre‐Matrix Composites

Preparation and properties of poly(propylene)‐poly(propylene) composites have been investigated. Poly(propylene) fibres of varying diameter have been incorporated in a random ethylene co‐poly(propylene). The composites prepared from the same semi‐crystalline polymer in the matrix and reinforcement have lead to inherently strong interfacial bonding between the two phases of the same polymer. The composites demonstrated enhanced stiffness, which increased with fibre diameter. The structure, thermal, static and mechanical properties of poly(propylene) long fibre reinforced random co‐poly(propylene) composites have been studied with reference to the fibre diameter. The matrix and fibre components retained their separate melting temperatures. After melting, the two phases remained separate and showed their individual crystallization temperatures on cooling, and melting temperatures on a second heating. The melting temperature of the poly(propylene) fibres increased after formation of the composites. The compression molding of the composites at a temperature below the melting temperature of the fibres caused annealing of the fibre crystals. By incorporation of long poly(propylene) fibre into random co‐poly(propylene), the glass transition, storage and static modulus have been found to be increasing and composite with the largest fibre diameter shows better properties. Transcrystallization of the matrix poly(propylene) was observed.

Optical microscopy of composites with fibre diameter 68 μm.     

Dramatic Improvements in Mechanical Properties of Poly(L‐lactide)/Silica Nanocomposites by Addition of Hyperbranched Poly(ester amide)

Biodegradable hyperbranched poly(ester amide) (HBP) was used as a compatibilizer to modify PLA/SiO₂ nanocomposites for the first time. The ternary composites displayed dramatically improved mechanical properties including excellent toughness and fairly high stiffness. TEM images revealed that an encapsulation structure was formed by HBP surrounding SiO₂ nanoparticles, and their surfaces became flocculent due to the migration process of silica. The linear viscoelastic behavior of the nanocomposites measured by parallel plate rheometer indicated that strong interface adhesion existed between PLA matrix and silica nanofiller after incorporating of HBP. The compatibilization effect of HBP and the enhanced mobility of nanoparticles contributed to the improved mechanical properties.

     

Structure and Mechanical Properties of Composites of Poly(6‐hexanelactam) Combining Solid Tribological Additives and Reinforcing Components

Summary: Three types of composites of polyamide 6 (PCL) with hybrid tribological additives were synthesized via anionic adiabatic “in situ” polymerization of 6‐hexanelactam (ε‐caprolactam) initiated with metallic sodium and activated with either cyclic trimer of phenyl isocyanate or diphenylmethane 4,4′‐diisocyanate. Combinations of the additives and their maximum applied concentrations (in wt.‐%) were the following: MoS₂/graphite(G)/oil(O) (5/16/9), short carbon fibers (CF)/G/O (5/20/10), and copper phthalocyanine (CPC) (7). Dynamic mechanical thermal analysis (DMTA) indicates a secondary (β) transition at about ?65 °C and the main (α) transition at temperatures close to 20 °C; the storage modulus passes through a shallow maximum as a function of the total content of additives. Tensile creep and indentation creep concurrently evidenced some increase in compliance with rising fraction of incorporated compounds. Stress‐strain tests in flexure show that flexural strength and toughness monotonically decreased with the content of MoS₂/G/O or CF/G/O, whereas the flexural modulus passed through a flat maximum. On the other hand, the strength and modulus were decreasing with CPC content, while toughness and Charpy impact tests showed some improvement.

Flexural toughness a_fU as a function of filler content C_ad in adiabatic anionic polymerization of 6‐hexanelactam.     

Fracture Toughness of Injection-Molded Poly(Butylene Terephthalate) Composites

Abstract:

The influences of various fiber amounts and injection molding process conditions on the fracture toughness of injection-molded short fiber-reinforced poly(butylene terephthalate) (PBT) composites were investigated. Three materials of various fiber amounts, neat PBT, 15 wt.%, and 30 wt.% short fiber-reinforced PBT composites, were used in this study. The compact tension (CT) specimens were prepared by various injection molding process conditions, wherein filling time, melt temperature, mold temperature, and packing pressure were design parameters used to measure fracture toughness. The morphology of the specimens, which consisted of frozen, intermediate, and core layers, was evaluated by scanning electron microscopy (SEM) and related to the fracture toughness. The fracture surfaces were also observed by SEM to understand the difference between the fracture mechanisms of neat PBT and fiber-reinforced PBT. It was found that the fracture toughness of neat PBT was significantly increased by the addition of short glass fibers. However, the variation of the injection molding design parameter had little effect on the fracture toughness. The fracture toughness depended on the thickness of the layers where fibers oriented perpendicular to the crack direction. The layer thickness was strongly affected by the fiber amounts.     

Properties of a poly(L‐lactic acid)/poly(D‐lactic acid) stereocomplex and the stereocomplex crosslinked with triallyl isocyanurate by irradiation

A poly(L ‐lactic acid) (PLLA)/poly(D ‐lactic acid) (PDLA) stereocomplex was prepared from an equimolar mixture of commercial‐grade PLLA and PDLA by melt processing for the first time. Crosslinked samples were obtained by the radiation‐induced crosslinking of the poly(lactic acid) (PLA) stereocomplex mixed with triallyl isocyanurate (TAIC). The PLA stereocomplex and its crosslinked samples were characterized by their gel behavior, thermal and mechanical measurements, and enzymatic degradation. The crosslinking density of the crosslinked stereocomplex was described as the gel fraction, which increased with the TAIC content and radiation dose. The maximum crosslinking density was obtained in crosslinked samples of PLA/3% TAIC and PLA/5% TAIC irradiated at doses higher than 30 kGy. The stable crosslinking networks that formed in the irradiated PLA/TAIC substantially suppressed the segmental mobility for the crystallization of single crystals as well as stereocomplex crystals. The crosslinking network also significantly improved the mechanical properties and inhibited the enzymatic degradation of crosslinked PLA/3% TAIC. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Mechanical properties of poly(ε‐caprolactone) and poly(lactic acid) blends

The aim of this work was to better understand the performance of binary blends of biodegradable aliphatic polyesters to overcome some limitations of the pure polymers (e.g., brittleness, low stiffness, and low toughness). Binary blends of poly(ε‐caprolactone) (PCL) and poly(lactic acid) (PLA) were prepared by melt blending (in a twin‐screw extruder) followed by injection molding. The compositions ranged from pure biodegradable polymers to 25 wt % increments. Morphological characterization was performed with scanning electron microscopy and differential scanning calorimetry. The initial modulus, stress and strain at yield, strain at break, and impact toughness of the biodegradable polymer blends were investigated. The properties were described by models assuming different interfacial behaviors (e.g., good adhesion and no adhesion between the dissimilar materials). The results indicated that PCL behaved as a polymeric plasticizer to PLA and improved the flexibility and ductility of the blends, giving the blends higher impact toughness. The strain at break was effectively improved by the addition of PCL to PLA, and this was followed by a decrease in the stress at break. The two biodegradable polymers were proved to be immiscible but nevertheless showed some degree of adhesion between the two phases. This was also quantified by the mechanical property prediction models, which, in conjunction with material property characterization, allowed unambiguous detection of the interfacial behavior of the polymer blends. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The effects on mechanical properties and crystallization of poly (l‐lactic acid) reinforced by cellulosic fibers with different scales

Bacterial cellulose (BC), microcrystalline cellulose (MCC), and bamboo cellulosic fibers (BCFs) were used to reinforce poly(l ‐lactic acid) (PLLA) based bio‐composites. The mechanical properties and crystallization of the composites were studied through mechanical testing, differential scanning calorimetry, X‐ray diffraction, scanning electron microscopy, and polarizing microscope. The incorporation of all three kinds of cellulose increased the stiffness of the composites compared to pure PLLA. The reinforcing effect of the MCC in the composites is most significant. The Young's modulus and impact toughness of the MCC/PLLA composites were increased by 44.4% and 58.8%, respectively. The tensile strength of the MCC/PLLA composites was increased to 71 MPa from 61 MPa of PLLA. However, the tensile strength of the composites reinforced with BCF or BC was lower than PLLA. The three kinds of cellulosic fibers improved the crystallization of PLLA. The BC with smallest size provided the composites with smallest grain and highest crystallinity. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41077.     

Preparation and characterization of a poly(methyl methacrylate) based composite bone cement containing poly(acrylate‐co‐silane) modified hydroxyapatite nanoparticles

The purpose of this study was to study the mechanical properties of poly(methyl methacrylate) (PMMA)‐based bone cement incorporated with hydroxyapatite (HA) nanoparticles after surface modification by poly(methyl methacrylate‐co‐γ‐methacryloxypropyl timethoxysilane) [P(MMA‐co‐MPS)]. PMMA and P(MMA‐co‐MPS) were synthesized via free‐radical polymerization. P(MMA‐co‐MPS)‐modified hydroxyapatite (m‐HA) was prepared via a dehydration process between silane and HA; the bone cement was then prepared via the in situ free‐radical polymerization of methyl methacrylate in the presence of PMMA and P(MMA‐co‐MPS)–m‐HA. Fourier transform infrared (FTIR) spectroscopy, ¹H‐NMR, and gel permeation chromatography were used to characterize the P(MMA‐co‐MPS). Thermogravimetric analysis and FTIR were used as quantitative analysis methods to measure the content of P(MMA‐co‐MPS) on the surface of HA. The effect of the proportion of m‐HA in the PMMA‐based bone cement on the mechanical properties was studied with a universal material testing machine. A 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide assay was also carried out to determine the cytotoxicity of the composite bone cement. The results showed that the surface modification of HA greatly improved the interaction between the inorganic and organic interfaces; this enhanced the mechanical properties of bone cement for potential clinical applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40587.     

Poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)‐based biocomposites reinforced with kenaf fibers

Biodegradable thermoplastic‐based composites reinforced with kenaf fibers were prepared and characterized. Poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV), produced by bacterial fermentation, was selected as polymeric matrix. To improve PHBV/fibers adhesion, low amount of a proper compatibilizing agent, obtained by grafting maleic anhydride onto PHBV, was added during matrix/fibers melt mixing (reactive blending). When compared with uncompatibilized composites, the presence of the compatibilizer induces a stronger interfacial adhesion and a more pronounced improvement of the mechanical properties. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007