Biomass carbon ratio of polymer composites included biomass or petroleum origin resources

The biomass carbon ratios of various polymer composites were studied. The biomass carbon ratios of polymer composites were estimated by the ratios of ¹⁴C to ¹²C measured by accelerator mass spectrometry (AMS) based on ASTM D 6866-08. The pretreatment conditions of the polymer composite of each constituent for the AMS measurement are described. The repeatability and accuracy of the biomass carbon ratio evaluation by AMS for the polymer composites with an inorganic filler, which are biomass-based plastics with mineral calcium carbonate and petroleum-based plastics with biobased calcium carbonate, such as shell powder or an organic filler, are discussed. The standard deviation of the polymer composite was less than 1%, and it was sufficiently lower compared with the limit of the AMS measurement (0.12%). Also, the biomass carbon ratio of each constituent of the polymer composite including the inorganic filler was significant based on the AMS measurement by changing the pretreatment conditions.     

Biocomposites of plasticized starch reinforced with cellulose crystallites from cottonseed linter

Environmentally friendly starch biocomposites were successfully developed using a colloidal suspension of cottonseed linter cellulose crystallite as a filler to reinforce glycerol plasticized starch (PS). The cellulose crystallites, having lengths of 350 +/- 70 nm and diameters of 40 +/- 8 nm on average, were prepared from cottonseed linters by acid hydrolysis. The dependence of morphology and properties of the PS-based biocomposites on cellulose crystallites content in the range from 0 to 30 wt.-% was investigated by scanning electron microscopy, differential scanning thermal analysis, dynamic mechanical thermal analysis, and measurements of mechanical properties and water absorption. The results indicate that the strong interactions between fillers and between the filler and PS matrix play a key role in reinforcing the resulting composites. The PS/cellulose crystallite composites, conditioned at 50% relative humidity, undergo an increase in both tensile strength and Young's modulus from 2.5 MPa for PS film to 7.8 MPa and from 36 MPa for PS film to 301 MPa. Further, incorporating cottonseed linter cellulose crystallites into PS matrix leads to an improvement in water resistance for the resulting biocomposites. The mechanical behaviors of the starch-based biocomposites as a function of cellulose crystallites content.     

Open-pore biodegradable foams prepared via gas foaming and microparticulate templating

Open-pore biodegradable foams with controlled porous architectures were prepared by combining gas foaming and microparticulate templating. Microparticulate composites of poly(epsilon-caprolactone) (PCL) and micrometric sodium chloride particles (NaCl), in concentrations ranging from 70/30 to 20/80 wt.-% of PCL/NaCl were melt-mixed and gas-foamed using carbon dioxide as physical blowing agent. The effects of microparticle concentration, foaming temperature, and pressure drop rate on foam microstructure were surveyed and related to the viscoelastic properties of the polymer/microparticle composite melt. Results showed that foams with open-pore networks can be obtained and that porosity, pore size, and interconnectivity may be finely modulated by optimizing the processing parameters. Furthermore, the ability to obtain a spatial gradient of porosity embossed within the three-dimensional polymer structure was exploited by using a heterogeneous microparticle filling. Results indicated that by foaming composites with microparticle concentration gradients, it was also possible to control the porosity and pore-size spatial distribution of the open-pore PCL foams.     

Effects of cellulose whiskers on properties of soy protein thermoplastics

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

Microfibrillated cellulose/cellulose acetate composites: Effect of surface treatment

Microfibrillated cellulose (MFC), which consists of a web‐like array of cellulose fibrils having a diameter in the range of 10–100 nm, was incorporated into a cellulose acetate (CA) matrix to form a totally biobased structural composite. Untreated and a 3‐aminopropyltriethoxysilane (APS) surface treated MFC was combined with a CA matrix by film casting from an acetone suspension. The effectiveness of the surface treatment was determined by infrared spectroscopy and X‐ray photoelectron spectroscopy. The Young's moduli of APS treated MFC composite films increase with increasing MFC content from 1.9 GPa for the CA to 4.1 GPa at 7.5 wt % of MFC, which is more than doubled. The tensile strength of the composite film increases to a maximum of 63.5 MPa at 2.5 wt % compared to the CA which has a value of 38 MPa. The thermal stability of composites with treated MFC is also better than the untreated MFC. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 153–161, 2010     

Homogenous synthesis of hydroxyethylcellulose in NaOH/urea aqueous solution

Hydroxyethylcellulose (HEC) was synthesized by a fully homogenous method from cellulose in 7.5 wt.-% NaOH/11 wt.-% urea aqueous solutions under mild conditions. HEC samples were characterized with NMR, SEC-LLS, solubility, and viscosity measurements. The MS and DS values of the obtained HEC samples are in the range from 0.54 to 1.44 and 0.45 to 1.14, respectively, and the relative DS values at C-2 and C-6 hydroxyl groups are slightly higher than those at C-3 hydroxyl groups. HEC samples are soluble in water starting from a MS of 0.57 and DS of 0.49, which display high viscosity in aqueous solutions. Moreover, a NaOH/urea aqueous solution is a stable system for cellulose etherification. In this way, we could provide a simple, pollution-free, and homogeneous aqueous solution system for synthesizing cellulose ethers.     

Structure and characteristics of film composites based on methyl cellulose,poviargol, and montmorillonite

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

Synthesis and characterization of poly(ε-caprolactone)-block-poly[N-(2-hydroxypropyl)methacrylamide] micelles for drug delivery

Amphiphilic block copolymers based on HPMA and ε-CL were synthesized by ring-opening polymerization of ε-CL followed by RAFT polymerization of HPMA. A copolymer composed of 34 kDa PHPMA and 8.5 kDa PCL associated into micelles with CMC of 5.4 μg · mL(-1) . A novel retinoid, 3-Cl-AHPC-OMe, was incorporated into micelles with 25 wt.-% loading by dialysis method. The effective diameter of drug loading micelles was 117 nm. Incubation of micelles in PBS at 37 °C indicated 86 wt.-% of the drug was released after 96 h. Cytotoxicity studies performed with C4-2 prostate cancer cells showed the IC(50) dose was 1.96 μM after 72 h of incubation, whereas the micelles without drug showed no cytotoxicity.     

A novel injectable poly(epsilon-caprolactone)/calcium sulfate system for bone regeneration: synthesis and characterization

A novel poly(epsilon-caprolactone)/calcium sulfate system was prepared and characterized in order to enhance calcium sulfate (gypsum) performance as bone graft substitute overcoming its brittleness and fast resorption rate. A poly(epsilon-caprolactone) (PCL) photo-crosslinkable derivative (PCLf) was synthesized by reaction of a low molecular weight PCL diol with methacryloyl chloride and confirmed by FT-IR and 1H NMR analyses. An injectable and easy mouldable mixture of PCLf and calcium sulfate hemi-hydrate (PCLf/CHS) was obtained. Thermal analyses and solvent extraction proved the occurrence of PCLf photo-crosslinking, even in the presence of CHS, in a time suitable for clinical applications. Swelling studies demonstrated that the encapsulation of the inorganic filler increases network hydrophilicity making it more permeable to water. Scanning electron microscopy, performed on crosslinked PCLf/CHS and on the same material after incubation in a PBS solution, showed the feasibility to obtain, in situ, gypsum entrapped into a degradable polymeric network. In vitro cytotoxicity tests, performed according to ISO 10993-5, proved that the developed system was not cytotoxic supporting its potential use in tissue engineering as a new, injectable, photocurable bone graft material. SEM micrograph of calcium sulfate di-hydrate (gypsum) entrapped in the PCL network.     

Effect of filler shape on mechanical properties of rigid polyurethane composites containing plant particles

The effect of types of fillers on mechanical properties of rigid polyurethane composite samples was investigated. Polyurethane (PU) composites were prepared using a molasses polyol (MP, a mixture of molasses and polyethylene glycol, Mw=200) diphenylmethane diisocyanate (MDI) and fillers. The following plant particles, bamboo powder, roast bamboo powder, wood meal, coffee grounds, ground coffee bean parchment and cellulose powder, were used as fillers. The mixture of MP and fillers was reacted with MDI by adding an adequate amount of acetone as a solvent. The content of fillers was defined as the ratio of filler weight to total weight of polyol and fillers. The filler content was varied from 10 to 90 wt%. Polyurethane (PU) composites were prepared using fillers with MP. Lengths of major axis and minor axis for each particle regarded as an ellipse were measured using an optical microscope. Averages of diameter and aspect ratio were derived for each plant particle. The relationships between these average values and the mechanical properties, such as strength and elastic modulus, determined by the compression tests were investigated. The effect of filler content was estimated using the apparent volume ratio which is determined as the ratio of the apparent volume of fillers to the reciprocal values of the apparent density of samples. The master curves of the relationships between the specific values of mechanical properties and the apparent volume ratio were obtained. It was found that the compression strength and the elastic modulus for composite samples with different fillers showed maximum values at average aspect ratio around 3. It was also found that the apparent volume ratio, where the mechanical properties showed maximums, decreases with increasing aspect ratio. Using master curves, it is possible to evaluate the mechanical properties of plant particle filled polyurethane composites are described.     

Depth-Dependent Indentation Microhardness Studies of Different Polymer Nanocomposites

Continuous depth sensing indentation microhardness measurements were performed to investigate the effect of filler content and dimensionality on the mechanical behaviour of different polymer nanocomposites. In 1D filler reinforced nanocomposites (such as PP/MWCNT system), both the hardness and the indentation modulus were found to appreciably increase up to a filler weight fraction of 1.6 wt.-%. Further addition of the filler changed the properties only insignificantly. In the nanocomposites with 2D filler (such as in PA6/LS) both the hardness and the indentation modulus increase notably with the addition of the filler and showed intense plasticity. In the investigated systems and composition range, the 3D filler (such as PP/OS2) showed no reinforcing effect at all. In was concluded that the 1D and 2D nanofillers play much more effective reinforcing role to improve the mechanical properties than the 3D fillers.     

Enhancement of dispersion stability of inorganic additives via poly(sodium-4-styrenesulfonate) treatment geared to hydrogel applications

This study reports the preparation of poly(sodium-4-styrene sulfonate) (PSS) treated bentonite and clinoptilolite to prevent the agglomeration and sedimentation of these inorganic fillers during the preparation of hydrogel. For this purpose PSS treated fillers were prepared by using various techniques (dip and dry, hydrothermal, one-step ball milling and ultrasonication methods). The most suitable technique for preparing these PSS treated inorganic fillers (abbreviated as BP-dip and CP-dip) was the dip and dry method. BP-dip and CP-dip based polyvinyl alcohol/polyvinylpyrrolidone (PVA/PVP) composite hydrogels were prepared using the freeze/thawing method after the addition of one of BP-dip and CP-dip inorganic fillers in various amounts. The swelling properties, stability behaviors and Rhodamine B (RhB) adsorption of the composite hydrogels were studied. It was found that the swelling degrees of CP-dip and BP-dip based composite hydrogels with 25 mg of filler were higher than that of all other samples. The kinetic mechanism of RhB adsorption process and the related characteristic kinetic parameters were investigated by Pseudo kinetic models. The adsorption kinetics results for RhB adsorption were found best fitted with pseudo-second-order kinetics model. The maximum RhB adsorption capacity was determined to be for PVA/PVP-CP-dip25, which was 3.3 times higher than that of the unfilled PVA/PVP hydrogel.     

FTIR spectroscopic investigation of inorganic fillers for composite DMFC membranes

An infrared spectroscopic investigation of inorganic fillers employed in composite perfluorosulfonic membranes has been carried out. The surface acidity of the fillers appears to influence the bending and stretching vibrational frequencies of the water physically adsorbed on the filler surface. The conductivity of composite membranes and maximum power density of direct methanol fuel cells (DMFCs) at 145 °C appear to be related to the characteristics of the water adsorbed on the filler particles. Inorganic fillers characterised by acidic properties undergo a strong interaction with water and enhance the DMFC performance at high temperature.     

Optimization of Lignin–Cellulose Nanofiber-Filled Thermoplastic Starch Composite Film Production for Potential Application in Food Packaging

The optimization of the production of thermoplastic starch (TPS) bionanocomposite films for their potential application in food packaging was carried out, according to the Box–Wilson Central Composite Design (CCD) with one center point, using Response Surface Methodology (RSM) and fillers based on lignin and nanofiber, which were derived from bamboo plant. The effects of the fillers on the moisture absorption (MAB), tensile strength (TS), percent elongation (PE) and Young’s modulus (YM) of the produced films were statistically examined. The obtained results showed that the nanocomposite films were best fitted by a quadratic regression model with a high coefficient of determination (R²) value. The film identified to be optimum has a desirability of 76.80%, which is close to the objective function, and contained 4.81 wt. % lignin and 5.00 wt. % nanofiber. The MAB, TS, YM and PE of the identified film were 17.80%, 21.51 MPa, 25.76 MPa and 48.81%, respectively. The addition of lignin and cellulose nanofiber to starch composite was found to have reduced the moisture-absorption tendency significantly and increased the mechanical properties of the films due to the good filler/matrix interfacial adhesion. Overall, the results suggested that the produced films would be suitable for application as packaging materials for food preservation.     

Investigation of the structure and swelling of poly(N-isopropyl-acrylamide-acrylamide) and poly(N-isopropyl-acrylamide-acrylic acid) based copolymer and composite hydrogels

We synthesized, thermo- and pH-sensitive gels and tested them as skin extenders. Our aim is the development of copolymer and composite hydrogels that, when implanted under the human skin, swell osmotically and thereby induce skin growth. In the course of the polymerization reaction, we produced copolymers with variable compositions, starting from different acrylic compounds [N-isopropyl-acrylamide (NIPAAm), acrylamide (AAm), and acrylic acid (AAc)]. The mechanical strength and the swelling stability of the gels are enhanced by the addition of fillers [Na-montmorillonite and Na-montmorillonites organophilized with alkylammonium ions (C_n-m.), n?=?4, 12, 18]. With this method we synthesized composite hydrogels. We observed that in the case of composites synthesized with the addition of fillers, relatively low filler contents (1–5 wt.%) resulted in more extensive swelling and stronger gel structure. During the experiments, the monomer composition (0/100–100/0 mol% NIPAAm/AAm or AAc) and the cross-link density (50–1500 mol%) of the gels (M/C ratio) and, in the case of composites, the quality and quantity of fillers are varied. The filler content of composites varies between 1 and 25 wt.%. The extent of swelling and the viscoelastic properties can be manipulated through the ratios of these parameters. In the case of certain copolymer and composite gels, values of desorption enthalpy (ΔH _m) corresponding to the actual water contents were also determined by thermoanalytical measurements (differential scanning calorimetry, DSC). Swelling values determined by gravimetry and enthalpies calculated from DSC measurements were found to be in good correlation. Even in the case of the relatively hydrophobic poly(NIPAAm)-based gels, an enthalpy value of 98.41 kJ/mol was obtained, which is twice the value measured in pure water (41.74 kJ/mol). Evaluation and comparison of the rheological and DSC results also allowed conclusions to be drawn concerning the types of interaction operating among the three components of the system, i.e., the polymer skeleton and the filler and water molecules.     

高锂离子电导的有机-无机复合电解质的渗流结构设计

固态聚合物电解质被认为是解决传统液态锂金属电池安全隐患和循环性能的关键材料,但仍然存在离子电导率低,界面兼容性差等问题。近年来,基于无机填料与聚合物电解质的高锂离子电导的有机-无机复合电解质备受关注。根据渗流理论,有机-无机界面被认为是复合电解质离子电导率改善的主要原因。因此,设计与优化有机-无机渗流界面对提高复合电解质离子电导率具有重要意义。本文从渗流结构的设计出发,综述了不同维度结构的无机填料用于高锂离子电导的有机-无机复合电解质的研究进展,并对比分析了不同渗流结构的优缺点。基于上述评述,展望了有机-无机复合电解质的未来发展趋势和方向。     

Structure and properties of regenerated cellulose/tourmaline nanocrystal composite films

Nanocomposite films were successfully prepared from cellulose and tourmaline nanocrystals with mean diameters of 70 nm in a 1.5 M NaOH/0.65 M thiourea aqueous solution by coagulation with 5 wt % CaCl₂ and then a 3 wt % HCl aqueous solution for 2 min. The structure and properties of the composite films were characterized by X‐ray diffraction, scanning electron microscopy, transmission electron microscopy, dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), and tensile testing. The results indicated that the tourmaline nanocrystals were dispersed in a cellulose matrix, maintaining the original structure of the nanocrystals in the composite films. The loss peaks (tan δ) in the DMA spectra and the decomposition temperatures in the DSC curves of the composite films were significantly shifted toward low temperatures, suggesting that the nanocrystals broke the partial intermolecular hydrogen bonds of cellulose, and this led to a reduction in the thermal stability. However, the nanocomposite films exhibited a homogeneous structure and dispersion of the nanocrystals. When the tourmaline content was in the range of 4–8 wt %, the composite films possessed good tensile strength (92–107 MPa) and exhibited obvious antibacterial action against Staphylococcus aureus. This work provides a potential way of preparing functional composite films or fibers from cellulose and nanoinorganic particles with NaOH/thiourea aqueous solutions. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 367–373, 2004     

New approach to filled polymers

Mechanopolymerization of pentabromobenzyl (mono)acrylate (PBB-MA) on the surface of inorganic fillers Mg(OH)₂ and CaCO₃ was studied. The role of activated surface of fillers was investigated using DSC and FTIR. The influence of milling time and of the filler chemical content on polymerization starting temperature and polymerization enthalpy was studied using DSC. It was shown that an increase of the filler concentration leads to a higher maximum conversion degree. The correlation between conversion kinetics and polymerization enthalpy of the material notpolymerized during milling was shown. This paper was presented on the Second Conference of The Israel Group of Mechanochemistry.     

Smooth and flexible filler-nanocellulose composite structure for printed electronics applications

A new type of micro/nanocomposite was made by using only micro fibrillated cellulose and inorganic fillers. This composite structure can contain up to 90% fillers being still mechanically stable and flexible. Calendering can be used to produce dense structures with extremely smooth surface. To study the effect of filler shape and type, both kaolin and precipitated calcium carbonate (PCC) based sheets were examined. Microscopy (cross-sectional and surface SEM images) and mechanical and morphological properties, including strength properties, surface roughness and dimensional stability as a function of moisture were analysed. After calendering the surface of the PCC containing sheets was smoother than that of photopaper and in the same level as reference plastic film Mylar A. The dimensional stability of the sheets was clearly better than that of paper sheets. The combination of a good dimensional stability with low surface roughness makes these structures potential for printed electronics applications, in which they could replace oil-based plastic substrates. Suitability for printed electronic applications was tested by inkjet printing conductors with silver nanoparticle ink. The sheet resistances of conductors printed on kaolin based sheets were close to those printed on plastic Mylar A film.     

Spirulina-based composites for 3D-printing

With material consumption increasing, the need for biodegradable materials derived from renewable resources becomes urgent, particularly in the popular field of 3D-printing. Processed natural fibers have been used as fillers for 3D-printing filaments and slurries, yet reports of utilizing pure biomass to 3D-print structures that reach mechanical properties comparable to synthetic plastics are scarce. Here, we develop and characterize slurries for extrusion-based 3D-printing comprised of unprocessed spirulina and varying amounts of cellulose fibers (CFs). Tuning the micro-morphology, density, and mechanical properties of multilayered structures is achieved by modulating the CF amount or drying method. Densified morphologies are obtained upon desiccator-drying, while oven incubation plasticizes the matrix and leads to intermediate densities. Freeze-drying creates low-density foam microstructures. The compressive strengths of the structures follow the same trend as their density. CFs are critical in the denser structures, as without the fibers, the samples do not retain their shape while drying. The compressive strength and strain to failure of the composites progressively increase with increasing filler content, ranging between 0.8 and 16 MPa and 12%–47%, respectively, at densities of 0.51–1.00 g/cm³. The measured properties are comparable to other biobased composites and commercial plastic filaments for 3D-printing.