Mechanical and Thermal Properties of PLLA/PCL Modified Clay Nanocomposites

Poly(l-lactic acid) (PLLA)/poly(caprolactone) (PCL) and two types of organoclay (OMMT) including a fatty amide and ocatdecylamine montmorillonite (FA-MMT and ODA-MMT) were employed to produce polymer nanocomposites by melt blending. Materials were characterized using X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), elemental analysis, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Mechanical properties were also investigated for these nanocomposites. The nanocomposites showed increasing mechanical properties and thermal stability. XRD results indicated that the materials formed nanocomposites. SEM morphology showed that increasing content of OMMT reduced the domain size of phase separated particles. TEM outcomes have confirmed the intercalated type of nanocomposite. Additionally, a solution casting process has been used to prepare these nanocomposites and characterized to compare these results with the above process.     

Enhancement of Tensile Strength and Flexibility of Polycaprolactone/Tapioca Starch Blends by Octadecylamine Modified Clay

Polycaprolactone/tapioca starch/octadecylamine modified clay (OMMT) nanocomposites were successfully prepared by melt blending. X-ray diffraction and transmission electron microscopy (TEM) of the products showed that they are nanocomposites of a mixture intercalated and exfoliated types. In addition, the TEM also revealed that the OMMT layers are homogeneously distributed in the polymer matrix. The presence of 1 php of OMMT improved the compatibility of the polymers in the blends which consequently increased the tensile strength of the blend of more than 60% and elongation at break of more than 1,000%.     

All-Cellulose Composite Fibers Obtained by Electrospinning Dispersions of Cellulose Acetate and Cellulose Nanocrystals

All-cellulose composite fibers were produced by electrospinning dispersions containing cellulose acetate (CA) and cellulose nanocrystals (CNCs). Precursor polymer matrices were obtained after dispersion of CA with different degrees of substitution in a binary mixture of organic solvents. The obtained fibers of CA loaded with CNCs had typical widths in the nano- and micro-scale and presented a glass transition temperature of 145?°C. The CA component was converted to cellulose by using alkaline hydrolysis to yield all-cellulose composite fibers that preserved the original morphology of the precursor system. Together with Fourier Transform Infrared Spectroscopy fingerprints the thermal behavior of the all-cellulose composite fibers indicated complete conversion of cellulose acetate to regenerated cellulose. Noticeable changes in the thermal, surface and chemical properties were observed upon deacetylation. Not only the thermal transitions of cellulose acetate disappeared but the initial water contact angle of the web was reduced drastically. Overall, we propose a simple method to produce all-cellulose composite fibers which are expected to display improved thermo-mechanical properties while keeping the unique features of the cellulose polymer.     

Biodegradability of PMMA Blends with Some Cellulose Derivatives

High polymer blends of Polymethyl methacrylate (PMMA) with cellulose acetate (CA) and Cellulose acetate phthalate (CAP) of varying blend compositions have been prepared to study their biodegradation behavior and blend miscibility. Films of PMMA–CA, and PMMA–CAP blends have been prepared by solution casting using Acetone and Dimethyl formamide(DMF) as solvents respectively. Biodegradability of these blends has been studied by four different methods namely, soil burial test, enzymatic degradation, and degradation in phosphate buffer and activated sludge degradation followed by water absorption tests to support the degradation studies. Degradation analysis was done by weight loss method. The results of all the tests showed sufficient biodegradability of these blends. Degradability increased with the increase in CA and CAP content in the blend compositions. The miscibility of PMMA–CA and PMMA–CAP blends have been studied by solution viscometric and ultrasonic methods. The results obtained reveal that PMMA forms miscible blends with either CA or CAP in the entire composition range. Miscibility of the blends may be due to the formation of hydrogen bond between the carbonyl group of PMMA and the free hydroxyl group of CA and CAP.     

Preparation of Cellulose Nanocrystals Using an Ionic Liquid

In this paper cellulose nanocrystals were prepared by treating microcrystalline cellulose with 1-butyl-3-methylimidazolium hydrogen sulphate ionic liquid. Cellulose nanocrystals, after separation from ionic liquid, were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR), Field emission scanning electron microscopy (FESEM) Transmission Electron Microscope (TEM) and Thermogravimetric analysis. XRD results showed no changes in type of cellulose after the treatment with ionic liquid, however, high crystallinity index was observed in the ionic liquid treated sample. Cellulose nanocrystals, having length around 50–300 nm and diameter around 14–22 nm were observed in the ionic liquid treated sample under FESEM and TEM, and similar patterns of peaks as that of microcrystalline cellulose were observed for cellulose nanocrystals in the FTIR spectra. The thermal stability of the cellulose nanocrystals was measured low as compare to microcrystalline cellulose.     

Performance Analysis of Rubber Seed Shell Activated Carbon Incorporated Polymeric Membrane for the Separation of Oil-in-Water Emulsion

Journal of Polymers and the Environment - In this study, pure cellulose acetate (CA) and rubber (Hevea brasiliensis) seed shell activated carbon (RSSAC) blended CA membranes were fabricated by the...     

The influence of degree of substitution on blend miscibility and biodegradation of cellulose acetate blends

In this account, we report our findings on blends of cellulose acetate having a degree of substitution (DS) of 2.49 (CA2.5) with a cellulose acetate having a DS of 2.06 (CA2.0). This blend system was examined over the composition range of 0–100% CA2.0 employing both solvent casting of films (no plasticizer) and thermal processing (melt-compressed films and injection molding) using poly(ethylene glycol) as a common plasticizer. All thermally processed blends were optically clear and showed no loss in optical quality after storage for several months. Thermal analysis and measurement of physical properties indicate that blends in the middle composition range are partially miscible, while those at the ends of the composition range are miscible. We suggest that the miscibility of these cellulose acetate blends is influenced primarily by the monomer composition of the copolymers. Bench-scale simulated municipal composting confirmed the biodestructability of these blends and indicated that incorporation of a plasticizer accelerated the composting rates of the blends.In vitro aerobic biodegradation testing involving radiochemical labeling conclusively demonstrated that both the lower DS CA2.0 and the plasticizer significantly enhanced the biodegradation of the more highly substituted CA2.5.While this work was in progress, Robert Gardner was struck with cancer and died on June 6, 1995. This paper is dedicated to his memory and to his contributions as a friend and colleague.     

PLA and Organoclays Nanocomposites: Degradation Process and Evaluation of ecotoxicity Using Allium cepa as Test Organism

In this study, nanocomposites of PLA and organoclays Cloisite 20A and Cloisite 30B were prepared by the melt intercalation method and the obtained samples were characterized by transmission electron microscopy (TEM). Since composting is an important proposal to the final disposal of biopolymers, the influence of clays on the hydrolytic degradation process of PLA was evaluated by visual analysis and monitoring of molecular weight after periods of 15 and 30 days of degradation in compost. After degradation of the materials in composting environment, the evaluation of cytotoxic, genotoxic and mutagenic effects of compost aqueous extract was carried out using a bioassay with Allium cepa as test organism. The TEM micrographs permitted the observation of different levels of dispersion, including exfoliated regions. In the evaluation of hydrolytic degradation it was noted that the presence of organoclays can decrease the rate of degradation possibly due to the barrier effect of clay layers and/or the higher degree of crystallinity in the nanocomposite samples. Nevertheless, even in the case of nanocomposites, the molecular weight reduction was significant, indicating that the composting process is favorable to the chain scission of PLA in studied materials. In the analysis performed by the bioassay using A. cepa as test organism, it was found that after degradation of the PLA and its nanocomposites the aqueous extract of compost samples induced a decreasing in the mitotic index and an increasing in the induction of chromosomal abnormalities. These results were statistically significant in relation to the negative control (distilled water). By comparing the results obtained for the nanocomposites in relative to pure polymer, there were no statistically significant differences. The types of the observed chromosomal aberrations indicated a possible genotoxic effect of the materials, which may be related to an aneugenic action of PLA degradation products.     

Preparation and Characterization of Hybrids of Cellulose Acetate Membranes Blended with Polysulfone and Embedded with Silica for Copper(II), Iron(II) and Zinc(II) Removal from Contaminated Solutions

Journal of Polymers and the Environment - With the objective to assess the suitability of cellulose acetate (CA), polysulfone (PSF) and silica (SiO2) for wastewater treatment, this work presents...     

A Comparative Study of Doum fiber and Shrimp Chitin Based Reinforced Low Density Polyethylene Biocomposites

The aim of this paper was to study the effects of reinforcing low density polyethylene (LDPE) by using bio-fillers (Doum cellulose or Shrimp chitin) on the mechanical properties. Both, Doum cellulose extracted frsom Doum leaves and Shrimp chitin extracted from shrimp co-products were compounded with LPDE without and with compatibilizer. The biocomposites were prepared by melt blending in a twin-screw extruder. Torsion and flexural tests were performed to investigate the impact of each reinforcement on the biocomposite mechanical properties. The SEM was carried out to study the filler/polymer interface adhesion. The present study has demonstrated that Doum fibers and shrimp chitin succeed in improving the mechanical properties of LPDE bio-composites. The results also showed that the use of maleic anhydride-grafted polyethylene as a compatibilizer improves filler adhesion/matrix and mechanical properties. This study exhibits that polyethylene composites based on Doum fibers or shrimp chitin can be used to replace the polyethylene materials in several fields like packaging and automotive industries.     

Biodegradable nanocomposites based on poly(butylene succinate)/organoclay

In this work, we try to incorporate the inorganic system into the biodegradable polymers to compose an organic/inorganic polymer hybrid. Various nanocomposites of poly(butylene succinates) (PBS) with different ratios of organically modified layered silicates (OMLS) prepared by solution blending were investigated. The OMLS used for the preparation of nanocomposites were functionalized ammonium salts modified montmorillonite. The effects of OMLS on the nanocomposites were investigated by XRD, TEM, DMA and TGA in the aspect of the d-spacing of clay, mechanical and thermal properties. Interestingly, all these nanocomposites exhibited improved properties when compared with the pristine PBS sample. XRD indicates that the layers of clay were intercalated by the modifiers, and the interlayer distance of organoclay in the nanocomposites could be extended to about 29.4 Å. Moreover, the thermal stability of the nanocomposites was enhanced by the addition of organoclay via TGA study, closely related to the organoclay content in the PBS matrix. DMA data shows that the storage and loss moduli were concurrently enhanced by the addition of organoclay as compared to the pristine PBS sample. Moreover, the glass transition temperatures also increased about 5 to 20 °C (from DMA, peak of tanδ) for the various organoclay-containing samples. The enhanced mechanical and thermal properties can be achieved from these organoclay modified-nanocomposites.     

The relationship between blend miscibility and biodegradation of cellulose acetate and poly(ethylene Succmate) blends

The miscibility of cellulose acetate (CA; degree of substitution = 2.5) and poly(ethylene succinate) (PES) has been investigated using a variety of thermal techniques and by solid-state carbon13 NMR spectroscopy. The blends containing greater than ca. 70% CA were found to be miscible. In the case of blends containing less than ca. 70% CA, a combination of thermal and NMR analyses suggests that these blends are not fully miscible on a 2.5- to 5-nm scale. On the scale which can be probed by dynamic mechanical thermal analysis (15 nm), the low-percentage CA blends exhibit “significant local concentration fluctuations≓. Investigation of the biodegradation of the blend components and of the blends revealed that PES degraded relatively rapidly and that CA degraded slowly. The blends degraded at a rate essentially identical to that of CA. Miscibility (75% CA blend) or crystallization of PES (30% CA blend) had no significant effect. These data suggest that a significant mode of degradation ófPES during composting involves chemical hydrolysis of the polymer followed by biological assimilation of monomers. Degradation of the blends is initiated in the amorphous phase. Because CA is a significant component of the amorphous phase, a small amount of CA significantly impacts the biodegradation rates of the blends.     

Utilization of Cellulosic Wastes in Textile and Garment Industries: 2. Synthesis and Characterization of Cellulose Acetate from Knitted Rag

Cellulose acetate (CA) was synthesized from knitted rag, a cellulosic waste of Textile and Garment industries, in the glacial acetic acid, and subsequently acetic anhydride (Ac₂O) in presence of concentrated H₂SO₄ reaction medium. A low to high substitution products were obtained from single step up to seven steps acetylation of cellulose. In this way, it was possible to produce low cost and different grades or substituted acetylation derivatives of cellulose. The synthesized CA was characterized and investigation of its physical characteristics was done. Solubility, acetyl content, acetic acid content, degree of substitution, and molecular weight of CA increased gradually with the increase of the number of reaction steps attaining optimum value at the fourth step. The acetyl and acetic acid content of CA were increased from 39.95 % to 44.25 %, and from 55.73 % to 61.73 % respectively. Similarly, degree of substitution and molecular weight of CA were increased from 2.47 to 2.94, and from 74,249 to 121,437 respectively.     

Biodegradation Properties of Poly-ε-caprolactone,Starch and Cellulose Acetate Butyrate Composites

Blending starches with polymers such as poly-ε-caprolactone (PCL) has been used as a route to biodegradable plastics. The addition of starch has a significant effect on all physical properties including toughness, elongation at break. On blending cellulose acetate butyrate (CAB) with starch and PCL, improvements in most physical and mechanical properties were observed. This is may be due to CAB acts as a compatibilizer between PCL and starch due to the presence of both hydroxyl groups (in starch and CAB) and ester carbonyls (in PCL and CAB). The presence of different compounds affects the way in which other components degrade. For example the structure of CAB within a starch and PCL combination might make the degradation rate different to that when starch was only mixed with PCL. To check whether this was the case, three combinations of different blends were used to calculate the rate of degradation of each of them separately. These degradation rate constants were then used to predict the theoretical degradation which was checked against the experimental value for other different combinations.     

Development of Cellulose Aerogel as a New Material for the Reduction of Harmful Substances in Cigarette Smoke

The current study proposes a novel and improved cigarette filtration design comprising cellulose nanofibers (CNFs) and powdered activated carbons (PACs) with different dry matter contents. The proposed filter samples were primarily analyzed to verify their applicability as cigarette filters via measurements and standard tests, such as SEM, BET, DSC, and airflow permeability analysis. The results were compared with the cellulose acetate (CA) sample used as a conventional cigarette filter. The preliminary results indicated noticeable improvement compared to the reference CA. Also, the cigarettes were tested using a smoking machine, and the filtered smoke was analyzed using GC–MS to evaluate the filters' performance in reducing the harmful substances present in the smoke. The results showed that the filters made of CNF and PAC significantly decreased the toxic substances compared with the reference but did not affect the nicotine substantially and therefore will not negatively impact the trance level of smokers.

     

Physical Properties of Chemically Modified Starch(RS4)/PVA Blend Films—Part 1

In this paper, we report on the physical properties of films that have been synthesized by using native corn starch (NS) and chemically modified starch (RS4). NS or RS4/PVA blend films were synthesized by using the mixing process and the casting method. Glycerol (GL), sorbitol (SO), and citric acid (CA) were used as additives. The chemically modified starch (RS4) was synthesized by using sodium trimetaphosphate (STMP) and sodium tripolyphosphate (STPP) as a crosslinker. Then, the RS4 thus synthesized was confirmed by using the pancreatin-gravimetric method, swelling power and an X-ray diffractometer (XRD). Tensile strength (TS), elongation (%E), swelling behavior (SB), and solubility (S) of the films were measured. The result of the measurements indicated the RS4-added film was better than the NS-added film. Especially, the RS4/PVA blend film with CA as an additive showed the physical properties superior to other films.     

Study of Thermo-Mechanical and Morphological Behaviour of Biodegradable PLA/PBAT/Layered Silicate Blend Nanocomposites

Poly (lactic acid) (PLA) and poly (butylene adipate-co-terephthalate) (PBAT) blend nanocomposites were prepared using melt blending technique followed by compression moulding. The blend nanocomposites were prepared with a variation of PBAT loading along with maleic anhydride and benzoyl peroxide ranging from 5 to 20 wt% along with two different commercially available nanoclays cloisite 93A and cloisite 30B (C30B) at 3 wt% loading. The maleic anhydride and benzoyl peroxide were used during the melt blending of the blend nanocomposites as a compatibilizer and as an accelerator respectively. Maleic anhydride used to enhance the compatibility of the PLA/PBAT blend and as well as the uniform adhesion of the nanoclays with them. The properties and characterizations of PLA matrix and the PLA/PBAT blend nanocomposites have been studied. The tensile strength, % elongation and impact strength increased with the preparation of PLA/PBAT blend nanocomposites as compared with PLA matrix. PLA/PBAT/C30B blend nanocomposites exhibited optimum tensile strength at 15 wt% of PBAT loading. Differential scanning calorimetry and thermogravimetric analysis also showed improved thermal properties as compared with virgin PLA. The wide angle X-ray diffraction studies indicated an increase in d-spacing in PLA/PBAT/C30B blend nanocomposite thus revealing intercalated morphology.     

Preparation and Properties of Thermoplastic Starch/Montmorillonite Nanocomposite Using N-(2-Hydroxyethyl)formamide as a New Additive

N-(2-Hydroxyethyl)formamide (HF) was synthesized efficiently and used as a new additive to prepare thermoplastic starch/montmorillonite nanocomposite (TPS/MMT). Here, HF acted as both plasticizer for TPS and swelling agent for MMT. The hydrogen bond interaction among HF, starch and MMT was proven by Fourier-transform infrared (FT-IR) spectroscopy. By scanning electron microscope (SEM), starch granules were completely disrupted. Atomic force microscopy demonstrated that partially exfoliated TPS/MMT nanocomposite was formed. The crystallinity of corn starch, MMT, HF-plasticized TPS (HTPS) and TPS/MMT nanocomposite was characterized by X-ray diffraction (XRD). Thermal stability of HTPS and TPS/MMT was determined by thermogravimetric analysis (TGA). The water resistance of TPS/MMT nanocomposite increased compared with that of pure HTPS. Tensile strengths of TPS/MMT nanocomposites were higher than those of HTPS, but just the reverse for elongations at break.     

The Effect of Fiber Pretreatment and Compatibilizer on Mechanical and Physical Properties of Flax Fiber-Polypropylene Composites

Recently, investigations have been conducted on the use of natural fibers as reinforcement in low-melting point thermoplastics to improve mechanical properties of composites. However, due to some limitations of natural fibers, composite formulation and processing parameters must be controlled to produce a product with improved properties. This study was conducted to investigate the influence of flax fiber loading, use of compatibilizer and pretreatment on physical and mechanical properties of compression-molded composite. In this study, untreated and treated (sodium hydroxide-treated and mild-bleached flax fibers) fibers at 15% and 30% of the total product mass were used in formulations. To investigate the effect of compatibilizer on product properties, maleic anhydride grafted polypropylene (MAPP) was added at 5% by mass in the formulations. After extrusion of composites formulations, they were formed using compression molding. Results indicated that using flax fiber in composites without pretreatment and compatibilizer could result into products with inferior physical and mechanical properties; this could be compensated by the use of a compatibilizer. However, the use of compatibilizer had some negative effects on some other physical properties like color and melt flow index (MFI).     

Preparation of Chitin/Cellulose Films Compatibilized with Polymeric Ionic Liquids

This paper reports the preparation of chitin/cellulose films compatibilized with polymeric ionic liquids. In-situ (co)polymerization of polymerizable ionic liquids, 1-(3-methacryloyloxypropyl)-3-vinylimidazolium bromide (1) and 1-methyl-3-vinylbenzylimidazolium chloride (3), was carried out in the presence of a radical initiator, AIBN, in the chitin/cellulose solution with ionic liquid solvents (1-butyl-3-methylimidazolium acetate and chloride, BMIMOAc and BMIMCl, respectively), followed by the appropriate procedure to give the desired films. The presence of the polymeric ionic liquid in the film was confirmed by the IR measurement. The powder X-ray diffraction analysis suggested that crystalline structures of the polysaccharides were largely disrupted in the film, as same as that of a chitin/cellulose film prepared by the AMIMOAc/BMIMCl system. These results were different from the XRD result of a chitin/cellulose film prepared by the 1-allyl-3-methylimidazolium bromide/BMIMCl system reported in our previous study, in which some crystalline structures were still remained in the film. Furthermore, the mechanical properties of the present films were evaluated by tensile testing, which were affected by the molar ratios of the polymeric ionic liquids to the polysaccharides and the compositional ratios of the two units 1 and 3.