Composites of poly(lactic acid)/poly(butylene adipate-co-terephthalate) blend with wood fiber and wollastonite: Physical properties,morphology, and biodegradability

Poly(lactic acid) (PLA) was first melt blended with five weight percentages (10–50 wt %) of poly(butylene adipate-co-terephthalate) (PBAT) on a twin-screw extruder and then injection molded. The blend at 30 wt % PBAT exhibited the highest impact strength and elongation-at-break without phase inversion. The 70/30 (w/w) PLA/PBAT blend with high toughness improvement was selected for preparing both single and hybrid composites using an organic filler, wood fiber (WF) and inorganic filler, wollastonite (WT) with a fix total loading at 30 parts per hundred of resin (phr) throughout the experiment. Five WF/WT (phr/phr) ratios for the composites were 30/0, 10/20, 15/15, 20/10, and 0/30. The prepared composites were investigated for the mechanical and thermal properties, melt flow index (MFI), morphology, flammability, water uptake, and biodegradability as a function of composition. All the composites showed a filler-dose-dependent decrease in the impact strength, elongation-at-break, MFI, and thermal stability, but an increase in the tensile and flexural modulus, tensile and flexural strength, antidripping ability, and water uptake compared with the neat blend. The addition of WF and WT was also found to promote the biodegradability of the PLA/PBAT blend. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47543.     

聚乙二醇改性淀粉/聚乳酸薄膜的结构与性质研究

将热塑性淀粉(TPS)与聚乙二醇(PEG)、聚乳酸(PLA)共混后,采用溶剂蒸发法制备出完全生物降解的聚乙二醇改性淀粉/聚乳酸薄膜(SPLA)。研究了SPLA膜的力学性能、耐水性,并对薄膜的结构进行了研究,结果表明聚乳酸可以明显改善淀粉基薄膜的耐水性与力学强度;当w(PLA)≤20%时,共混物各组分间有较好的相容性。SPLA膜的玻璃化转变温度低于淀粉和聚乳酸,XRD显示共混膜中淀粉和聚乳酸的颗粒结晶结构均受到破坏。     

Incorporating amylopectin in poly(lactic acid) by melt blending using poly(ethylene‐co‐vinyl alcohol) as a thermoplastic carrier. II. Physical properties

This study adds to a previous morphological work (paper I) with further characterization of the developed poly(lactic acid) (PLA) blends containing amylopectin, which made use of an ethylene‐vinyl alcohol copolymer (EVOH) as a melt‐compoundable carrier for the polysaccharide in the biopolyester. The effect of using glycerol as compatibilizer was also characterized. Water and oxygen transport parameters, mechanical properties, and comparative biodegradability tests were evaluated for the blends. From the results, the barrier properties to oxygen were only seen to improve at 0%RH and mostly for the PLA‐EVOH blends, which furthermore showed a positive deviation from the rule of mixtures. At high relative humidity, the blends showed somewhat poorer barrier performance due to the comparatively higher improvement in barrier of the neat PLA at 80% RH. Interestingly, room temperature biodegradability testing suggested that low additions of the blending elements seemed to facilitate the biodegradability of the biopolyester. Despite the fact that properties were not so dramatically improved, incorporating renewable resources within PLA seems as a potentially viable route to reduce PLA supply dependency, retain good optical properties and to overcome some drawbacks associated to the use of this biopolyester. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

马来酸酐/二乙烯基苯接枝聚乳酸对微晶纤维素/聚乳酸复合材料性能的影响

研究了马来酸酐(MAH)/二乙烯基苯(DVB)接枝聚乳酸(PLA-g-DVB/MAH)对微晶纤维素(MCC)/聚乳酸(PLA)复合材料性能的影响。首先采用熔融接枝法,将DVB作为MAH的共聚单体接枝到PLA分子链上制备PLA-g-DVB/MAH接枝聚合物,然后以PLA-g-DVB/MAH为相容剂,采用注射成型法制备MCC/PLA复合材料。利用FTIR对PLA-g-DVB/MAH进行表征,探究了PLA-g-DVB/MAH对MCC/PLA复合材料流变及力学性能的影响。结果表明,MAH成功接枝到PLA上,并得到接枝聚合物PLA-g-DVB/MAH;添加PLA-g-DVB/MAH后,MCC/PLA复合材料的储能模量、复数黏度、平衡扭矩以及剪切热都有明显升高;PLA-g-DVB/MAH的添加有利于改善MCC和PLA的界面相容性,进而提高了MCC/PLA复合材料的力学性能。     

Mechanical,barrier, and thermal properties of poly(lactic acid)/poly(trimethylene carbonate)/talc composite films

Poly(l ‐lactic acid) (PLA) is now a very attractive polymer for food packaging applications. In this study, PLA/poly(trimethylene carbonate) (PTMC)/talc composite films were prepared by solvent casting. The influence of the talc loading (0, 1, 2, and 3 wt %) on the phase morphology of the PLA/PTMC/talc composites and the improvement in the resulting properties are reported in this article. The scanning electron microscopy images of the composite films demonstrated good compatibility between the PLA and PTMC, whereas talc was not thoroughly distributed in the PLA matrix at talc contents exceeding 3 wt %. The tensile strength and elongation at break of the composite films significantly improved (p < 0.05). On the contrary, the water vapor permeability and oxygen properties of the composite films decreased by 24.7 and 39.2%, respectively, at the 2 wt % talc loading. Differential scanning calorimetry showed that the crystallinity of the PLA phase increased with the presence of talc filler in the PLA/PTMC/talc composites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40016.     

Mechanical properties of poly(lactic acid) and wheat starch blends with methylenediphenyl diisocyanate

Poly(lactic acid) (PLA) and wheat starch are biodegradable polymers derived from renewable sources. A previous study showed that thermally blending starch and PLA in the presence of methylenediphenyl diisocyanate (MDI) enhanced the mechanical properties of the blends. In this work, blends of PLA with various levels of wheat starch and MDI were hot mixed at 180°C then hot‐pressure molded at 175°C to form test specimens. The blends were characterized for mechanical properties, fracture microstructure, and water absorption. Pure PLA had a tensile strength of 62.7 MPa and elongation of 6.5%. The blend with 45% wheat starch and 0.5 wt % MDI gave the highest tensile strength of about 68 MPa with about 5.1% elongation. The blend with 20% starch and 0.5 wt % MDI had the lowest tensile strength of about 58 MPa with about 5.6% elongation. Dynamic mechanical analysis showed that storage modulus increased and tan δ decreased as starch level increased, but almost leveled off when starch level reached 45% or higher. Water absorption of the blends increased significantly with starch content. Yet the blend, if water proofed on its surface, has potential for short‐term disposable applications. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1257–1262, 2002; DOI 10.1002/app.10457     

Carotenoids extracts as natural colorants in poly(lactic acid) films

The use of vivid packaging colors is a strategy to attract consumers' attention and interest. In this context, the awareness of harmful effects caused by the use of synthetic colorants has led to an increasing interest in naturally derived alternatives. The use of carotenoids as colorants for polymeric materials represents an environmentally friendly way of obtaining colored packaging. The incorporation of carotenoids extracts rich in bixin, lycopene, and β‐carotene into poly(lactic acid) films was evaluated, where the presence of carotenoids (100 μg/g) reduced oxygen permeability and presented a lubricant effect, increasing films elasticity up to 50%. No effect on films crystallinity was observed. Carotenoids reduced films transparency and bixin was the most stable carotenoid at dark and light conditions. The color stability of films, evaluated through kinetic parameters of color degradation, presented Chroma half‐life times (40 °C/light) of 111, 51, and 5 days for bixin, lycopene, and β‐carotene, respectively. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46585.     

Barrier properties of poly(lactic acid) and its morphological changes induced by aroma compound sorption

The barrier properties of poly(lactic acid) (PLA) play a key role in food packaging applications. For their optimization, the influence of crystallinity on the barrier properties of PLA and the interaction of PLA with the aroma compound ethyl acetate were investigated. PLA film samples with various crystallinities were fabricated by flat die extrusion and thermocompression and compared to PLA Biophan^?. The degree of crystallinity had no effect on the oxygen permeability. However, an increase of crystallinity caused a decrease in ethyl acetate sorption. The sorption isotherm of ethyl acetate obtained using microgravimetry showed a steep increase with increasing aroma activity, a form which is consistent with a plasticization effect. This behaviour was verified using differential scanning calorimetry and dynamic mechanical analysis. Sorption caused a marked decrease in the glass transition temperature well below room temperature to approximately 0 °C. Furthermore, PLA underwent a solvent‐induced crystallization when equilibrated in ethyl acetate atmosphere at an activity of 0.5. The results obtained show the importance of considering possible interactions between polymer and foodstuff during the optimization step of polymeric materials for food packaging applications. Copyright © 2010 Society of Chemical Industry     

Dynamic mechanical and thermal properties of plasticized poly(lactic acid)

The blends of low molecular weight triacetin (TAC) and oligomeric poly(1,3‐butylene glycol adipate) (PBGA) were used as multiple plasticizers to lubricate poly(lactic acid) (PLA) in this study. The thermal and mechanical properties of plasticized polymers were investigated by means of dynamic mechanical analysis and differential scanning calorimetry. Atomic force microscopy (AFM) was used to analyze the morphologies of the blends. Multiple plasticizers were effective in lowering the glass transition temperature (T_g) and the melting temperature (T_m) of PLA. Moreover, crystallinity of PLA increased with increasing the content of multiple plasticizers. Tensile strength of the blends decreased following the increasing of the plasticizers, but increased in elongation at break. AFM topographic images showed that the multiple plasticizers dispersed between interfibrillar regions. Moreover, the fibrillar crystallite formed the quasicrosslinkings, which is another cause for the increase in elongation at break. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1583–1590, 2006     

Biodegradable polymer blends of poly(lactic acid) and poly(ethylene glycol)

Poly(lactic acid) (PLA) and poly(ethylene glycol) (PEG) were melt-blended and extruded into films in the PLA/PEG ratios of 100/0, 90/10, 70/30, 50/50, and 30/70. It was concluded from the differential scanning calorimetry and dynamic mechanical analysis results that PLA/PEG blends range from miscible to partially miscible, depending on the concentration. Below 50% PEG content the PEG plasticized the PLA, yielding higher elongations and lower modulus values. Above 50% PEG content the blend morphology was driven by the increasing crystallinity of PEG, resulting in an increase in modulus and a corresponding decrease in elongation at break. The tensile strength was found to decrease in a linear fashion with increasing PEG content. Results obtained from enzymatic degradation show that the weight loss for all of the blends was significantly greater than that for the pure PLA. When the PEG content was 30% or lower, weight loss was found to be primarily due to enzymatic degradation of the PLA. Above 30% PEG content, the weight loss was found to be mainly due to the dissolution of PEG. During hydrolytic degradation, for PLA/PEG blends up to 30% PEG, weight loss occurs as a combination of degradation of PLA and dissolution of PEG. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1495–1505, 1997     

分子筛改性可降解材料聚乳酸的研究

将吸附有聚乳酸齐聚物的分子筛同工业级聚乳酸在双螺杆挤出机中造粒,制备了分子筛改性聚乳酸材料。研究了分子筛对聚乳酸力学性能的影响,添加量在7%~9%左右时可以起到最好的增强效果;复合材料可以在土壤中自然降解,增加分子筛添加量可以加快复合材料的降解。     

Epoxidized soybean oil‐plasticized poly(lactic acid) films performance as impacted by storage

This study examined the effect of storage time at room temperature on the melt viscosity, thermal, and tensile properties of epoxidized soybean oil plasticized poly(lactic acid) (PLA) films manufactured through a cast extrusion process. Infrared results indicate that plasticizer migration to the surface of the film occurred after only 30 days of storage, which significantly affected the performance of plasticized films. While the melt viscosity, glass transition temperature, degree of crystallinity, tensile strength, and modulus increased, the elongation at break and energy to break decreased with storage time up to 30 days and all properties remained constant thereafter. However, the ability of stored plasticized film to cold crystallize remained unaffected since both the cold crystallization temperature and melting temperature were not affected during storage. Although plasticized film lost some flexibility after only 30 days of storage due to plasticizer migration to the surface of the film, sufficient plasticization performance still remained in plasticized PLA films for flexible packaging application even after a long storage period at ambient conditions. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43201.     

Influence of recycling of poly(lactic acid) on packaging relevant properties

The most promising representative of biodegradable plastics in packaging applications is polylactide (PLA). Despite this, there is only a small market of PLA in Europe. Reasons for that are the high price of PLA raw material and the lack of knowledge of the behavior in packaging applications. It has a number of peculiarities so producers of plastics packaging hesitate to use it. Like other polyesters, it can degrade at increased temperatures in the presence of moisture by hydrolysis whereby it loses its physical and chemical properties. In all production processes, production waste is generated (i.e., stamping grids or edge trim). In most cases, this waste is used. It is not known in detail, how an internal recycling process will influence the final product properties. One problem is hydrolysis by which the production waste is partially degraded. Target of this study is to analyze the recycling process of PLA within the context of necessary process adaptions and the effects upon ecological efficiency. Films for packaging containing multiple types and amounts of production waste will be produced by extrusion and tested concerning their mechanical properties. The analysis of the recycling behavior showed that internal PLA production waste is well suitable for recycling. The influence of the recycling on the molecular weight is negligible. The effect on the viscosity and thus on the extrusion process is higher. Packaging relevant properties like mechanical or optical properties are hardly influenced. Especially recycling with a recycling quota of up to 50% has an insignificant effect on the film properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41532.     

Processing and characterization of poly(lactic acid) films plasticized with commercial adipates

The high brittleness of Poly(lactic acid) is a major drawback for flexible food packaging applications. The aim of this work is to evaluate the potential use of commercial adipates as PLA plasticizers to obtain transparent films with enhanced mechanical properties. Processing conditions were optimized. The effect of plasticizers was characterized by a decrease on the glass transition temperature and an increase in PLA chains mobility, which induced crystallization on heating. Thermal stability was not significantly affected, and mechanical properties showed an increase in ductility with the plasticizer content. Oxygen transmission rate was also measured to evaluate the effect of the microstructures generated by the presence of these additives in PLA‐based films. The monomeric adipate presented lack of homogeneity that makes films plasticized with this additive not useful for the intended application. Good compatibility was observed between polyadipates (up to 20 wt %) and the matrix, making them promising materials for biodegradable films manufacturing. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Thermomechanical properties of poly(lactic acid) films reinforced with hydroxyapatite and regenerated cellulose microfibers

Novel composite films constituted of poly(lactic acid) (PLA), hydroxyapatite (HAp), and two types of regenerated cellulose fillers—particulate and fibrous type—were produced by melt extrusion in a twin‐screw micro‐compounder. The effect of the film composition on the tensile and dynamic mechanical behavior and the HAp dispersion in the PLA matrix were investigated thoroughly. Appearance of crazed regions and prevention of HAp aggregation in the PLA matrix were elucidated in the composites with up to 15 wt % particulate cellulose content, which was the main reason for only slight reduction in the tensile properties, and consequently trivial degradation of their pre‐failure energy absorption as compared to neat PLA films. Superior dynamical energy storage capacities were obtained for the particulate cellulose modified composites, while their fibrous counterparts had not as good properties. Additionally, the anisotropic mechanical behavior obtained for the extruded composites should be favorable for use as biomaterials aimed at bone tissue engineering applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40911.     

Effects of moisture content and heat treatment on the physical properties of starch and poly(lactic acid) blends

Starch, a hydrophilic renewable polymer, has been used as a filler for environmentally friendly plastics for about 2 decades. Starch granules become swollen and gelatinized when water is added or when they are heated, and water is often used as a plasticizer to obtain desirable product properties. The objective of this research was to characterize blends from starch and poly(lactic acid) (PLA) in the presence of various water contents. The effects of processing procedures on the properties of the blends were also studied. Blends were prepared with a lab‐scale twin‐screw extruder, and tensile bars for mechanical testing were prepared with both compression and injection molding. Thermal and mechanical properties of the blends were analyzed, and the morphology and water absorption of the blends were evaluated. The initial moisture content (MC) of the starch had no significant effects on its mechanical properties but had a significant effect on the water absorption of the blends. The thermal and crystallization properties of PLA in the blend were not affected by MC. The blends prepared by compression molding had higher crystallinities than those prepared by injection molding. However, the blends prepared by injection molding had higher tensile strengths and elongations and lower water absorption values than those made by compression molding. The crystallinities of the blends increased greatly with annealing treatment at the PLA second crystallization temperature (155°C). The decomposition of PLA indicated that PLA was slightly degraded in the presence of water under the processing temperatures used. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3069–3082, 2001     

Biodegradable antimicrobial films based on poly(lactic acid) matrices and active azo compounds

Using solvent casting and melt compounding methods, we realized antibacterial and antifungal poly(lactic acid)‐based films by introducing different percentages of antimicrobial azo dyes into polymer matrices. Concentration up to 0.01% (w/w) of azo compounds permitted the preparation of antimicrobial and transparent films. The thin films retained the properties of the pure PLA matrices, such as glass transition temperature, flexibility, and amorphous nature. The films exhibited antimicrobial activity and the capability to inhibit biofilms formation of Staphylococcus aureus and Candida albicans. Spectrophotometric investigation of azo compounds release from the polymer matrices confirmed that the materials might have applications in fields where an intrinsic antimicrobial ability of the material is required, such as biomedical tools, biodegradable antibacterial coatings, and films for active packaging. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42357.     

聚乳酸/聚乙二醇共混物的结晶与降解行为

针对聚乳酸（PLLA）亲水性差、降解周期长的问题,利用与亲水性高分子聚乙二醇（PEG）共混的方法对其进行改性。采用转矩流变仪制备了不同组成的PLLA/PEG共混物颗粒,系统研究了PLLA/PEG共混物的结晶和熔融、亲水性和在酸碱介质中的降解行为。结果表明,PEG的加入增强了共混物中PLLA的结晶能力,提高了PLLA在降温过程中的熔融结晶温度。PLLA/PEG共混物在等温结晶中表现出比纯PLLA更快的结晶速度。通过改变PLLA/PEG共混物的组成,可调控材料的表面亲水性和降解速率。随着PEG含量的增多,PLLA/PEG共混物的表面接触角降低。PLLA与PLLA/PEG共混物均可在水溶液中降解,共混物的降解速率高于纯PLLA,随着PEG含量的升高和降解液中酸碱浓度的提高,PLLA/PEG共混物的降解速率加快。     

Mechanical,thermal and combustion properties of intumescent flame retardant biodegradable poly (lactic acid) composites

ABSTRACT

Despite extraordinary mechanical properties and excellent biodegradability, poly (lactic acid) (PLA) still suffers from a highly inherent flammability, restricting its applications in the electric and automobile fields. Although a wide range of flame retardants have been developed to reduce the flammability, they normally compromise the mechanical strength of PLA. In this study, a series of composites based on PLA, have been prepared by melt-blending with intumescent flame retardants (IFRs). The morphology, thermal stability and burning behaviour of the composites were investigated using a scanning electron microscope–energy dispersive spectrometer (SEM–EDS), thermogravimetric analysis (TGA), the limiting oxygen index (LOI), vertical burning (UL-94) and the cone calorimeter test (CCT). The LOI value reached 38.5% and UL-94 could pass V-0 for the PLA/IFR composite containing only 12 wt-% IFR. The dispersion of IFR in PLA was observed using SEM–EDS. A significant improvement in fire retardant performance was observed for the PLA/IFR composite from the CCT (reducing the heat release rate and the total heat release). More importantly, compared to pure PLA, the addition of IFR did not seriously deteriorate the mechanical properties of the material.     

Fabrication and characterization of sucrose palmitate reinforced poly(lactic acid) bionanocomposite films

Environmental issues concerning petroleum‐based polymers have begun a growing emphasis to utilize sustainable poly(lactic acid) (PLA) based packaging. However, PLA has its own limitations such as brittleness, high gas permeabilities and slow crystallization rate. With the aim to alleviate these limitations, we made a maiden effort to use a food additive, sucrose palmitate (SP) as eco‐friendly filler for fabrication of PLA based bionanocomposites. FTIR analysis elucidated the presence of hydrogen bonding and intermolecular interaction between PLA and reinforcement. Ordered orientation of the SP in the PLA matrix visualized by TEM analysis revealed uniform dispersion of SP filler into PLA matrix. DSC and XRD results confirmed that the incorporated bio‐filler acted as a nucleating agent and thus partially contributed towards the crystallinity of PLA‐SP bionanocomposites. Enhancement in the tensile strength and elongation at break up to 83 and 56% respectively is obtained. The best positive influence for the oxygen barrier was confirmed for the PLA‐SP bionanocomposite film where the reduction in oxygen permeability by 69% is achieved in comparison to pure PLA. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41320.