The influence of microcrystalline cellulose grade on shape and shape distributions of pellets produced by extrusion-spheronization.

In this study, five microcrystalline cellulose (MCC) grades were physically characterized and their extrusion-spheronization behaviours were characterized in terms of water requirements and pellet shape profiles. It was found that the MCC grades differed significantly in the physical properties investigated. Physical properties of MCC were found to influence the water requirement for extrusion-spheronization. MCC grades of higher bulk densities, lower porosities and water retentive capacities required less water to produce pellets of equivalent size. These MCC grades were also found to produce pellets of lower sphericity and wider shape distributions. Packing of MCC particles within the agglomerate played a role in determining amount of water retention and pellet rounding during spheronization. However, there was a limit to the influence of packing density on the rate of pellet rounding because poor packing resulted in higher water retentive capacity, which also limited the rate of rounding.     

1H-NMR Relaxation of Water Molecules in the Aqueous Microcrystalline Cellulose Suspension Systems and Their Viscosity

An intensive study for aqueous microcrystalline cellulose (MCC) suspensions was carried out in view of the relationship between a viscosity and a 1H spin-spin relaxation time (T2) of water. An investigation was carried out for four suspension systems with the different particle size distributions. The proton mole ratio () of bound water against MCC particles and T2 of bound water (T2,b) were evaluated from the T2 values obtained by Carr-Purcell- Meiboom-Gill (C.P.M.G) method and those by solid echo method, respectively. As a result of these analyses, the T2,b value for the aqueous MCC suspension was evaluated as 5 × 10–3 s and it was found that the system having a larger tended to show a higher viscosity. By relating the above results to the observation of the suspensions by an optical microscope, it was concluded that a network formed by MCC particles plays an important role in generating a high viscosity of MCC suspension, and that an averaged mobility of water molecules is sensitively affected by the network structure.     

Polyethylene oxides

The aim of this study was to study tablet formation of polyethylene oxides (PEOs) with different molecular masses by means of 3D modeling and comparing the results to those of other more traditional techniques, such as Heckel analysis, analysis by the pressure- time function and energy analysis. The molecular masses ranged between 400,000 and 7,000,000 Da. Material properties, such as water content, particle size and morphology, and glass transition temperature were also studied. To complete this study, elastic recovery dependent on maximum relative density and time were determined. Furthermore, the crushing force of the tablets and their morphology were analyzed. The PEOs consist of smooth edged particles of irregular shape; the particle size is similar to one type of MCC, namely Avicel PH 200. The PEOs are much more ductile during compression than MCC. Elastic recovery after tableting is higher than that for tablets made from MCC and continues for some time after tableting. The crushing force of the resulting tablets is low. In conclusion, with regards to direct compression the PEOs do not appear to be useful as sole tableting excipients.     

Effects of Microcrystalline Cellulose on Suspension Stability of Cocoa Beverage

The rheological properties and particle size distributions of cocoa beverage as well as aggregate structures of solid particles were studied to elucidate the effects of microcrystalline cellulose (MCC) on suspension stability of solid particles in cocoa beverage. Fluidity curve, dynamic viscoelasticity, particle size distribution, and SEM observation were made for beverage samples containing 0.1–0.5 wt% MCC and 11 model samples with various combinations of six ingredients. This revealed that cocoa and MCC particles are highly cohered into an aggregate and the aggregated particles further interact weakly with the milk component, leading to stabilization of the whole system of cocoa beverage.     

Thermal degradation behaviors of polybenzoxazine and silicon-containing polyimide blends

Thermal behaviors of polymer blends between common-type polybenzoxazine (PBA-a) and polysiloxane-block-polyimide (SPI) were studied using Dynamic Mechanical Analysis (DMA) and Thermogravimetric Analysis (TGA). The polymer blends showed only one glass-transition temperature (T_g) that increased as the content of SPI increased. Synergistic behavior in the char formation of the alloys was clearly observed. The DTG curves showed three stages and two stages of decomposition reaction in neat PBA-a and SPI, respectively. For the blending systems with 25 wt%, 50 wt%, and 75 wt% of SPI, the DTG thermograms of the blends exhibited four stages of thermal decomposition reaction. The apparent activation energies (E_a) of each step were determined using Kissinger method, Flynn-Wall-Ozawa method and Coats-Redfern method. The type of solid state mechanism was determined by Criado method. From the calculation, the solid state thermal degradation mechanism is proposed to be F1 (random nucleation with one nucleus on the individual particle) type for PBA-a, SPI, and their blends.     

The effect of dynamic vulcanization on the properties of polymer-elastomer blends containing crumb rubber

The influence of dynamic vulcanization on the amount of the sol fraction, the crosslink density, the melt flow index, and the mechanical properties of ternary (isotactic polypropylene-rubber-crumb rubber) and binary (rubber-crumb rubber) blends was studied. Two types of ethylene-propylene-diene terpolymer (elastomer) were used as the rubber component, the oil-free elastomer and the elastomer extended with paraffin oil during its synthesis. The blends were vulcanized in the presence of a sulfur accelerating system. It was shown that blends with crumb rubber having a particle size of less than 0.1 mm exhibited the best mechanical and rheological characteristics. The introduction of crumb rubber into thermoplastic elastomers that contain the oil-free ethylene-propylene-diene terpolymer leads, at a certain ratio of the components, to a rise in the melt flow index, regardless of the crumb-rubber particle size and of whether the rubber component was vulcanized.     

Comparing microcrystalline with spherical nanocrystalline cellulose from waste cotton fabrics

Microcrystalline cellulose (MCC) and spherical nanocrystalline cellulose (SNCC) were successfully prepared from waste cotton fabrics through acid hydrolysis. The comparative analysis of the morphology and structure between the obtained MCC and SNCC was carried out. The SNCC suspension exhibited higher stability than the MCC suspension. Transmission electron microscopy in combination with atomic force microscopy showed that the cellulose nanospheres with average size of 35?nm were achieved, while the average particle size of MCC was 49?μm. The MCC and SNCC had similar functional groups and crystalline structure as confirmed by Fourier transform infrared spectroscopy and X-ray diffraction analysis, respectively. Viscometric average molecular weight measurement and thermo gravimetric analysis indicated that the degree of polymerization and thermal stability of SNCC was lower than that of MCC. These results should improve understanding of the characteristics of MCC and SNCC derived from waste cotton fabrics and lead to many new applications.     

污泥与煤和煤矸石共燃特性研究

利用STA 409 PC型同步热分析仪,对煤、煤矸石和污泥不同质量比样品的燃烧过程进行了热重分析。结果表明,单一煤和煤矸石的DTG曲线都只有一个明显的失重峰,污泥的DTG曲线有两个明显的失重峰,而混合物的DTG曲线都有两个失重峰。通过分析不同样品的混燃过程,发现随着煤所占质量比的增加,最大失重峰速率所对应的温度都有所降低。煤、煤矸石、污泥及其混合物的活化能为16.93kJ/mol～109.89kJ/mol。随着污泥所占质量比的增加,混合物的着火温度有所降低,当达到70%时,污泥与煤混合物的着火点接近单一污泥的着火点。     

A study of the mechanical, thermal and morphological properties of microcrystalline cellulose particles prepared from cotton slivers using different acid concentrations

Microcrystalline cellulose (MCC) particles are mostly prepared by acid hydrolysis of various agro sources. Acid hydrolysis is usually carried out with high concentration (64 wt%) of sulfuric acid. Here, an attempt has been made to optimize lower acid concentrations which can effectively produce MCC particles. In this work, different concentrations of sulfuric acid (20, 30, 35, 40, 47 and 64 wt%) have been used to prepare MCC particles, which have been characterized by XRD, particle size analysis, scanning electron microscopy, transmission electron microscopy, nanoindentation and thermogravimetric analysis. MCC prepared with 35 and 47% sulfuric acid (MCC 35 and MCC 47) had finest particle size and fibrils were produced in the range of 15–25 nm. MCC 20 showed wide particle size distribution, indicating low breakdown of the cellulose chains. The energy absorption behavior and mechanical properties of the MCC pellets were determined by nanoindentation test for the first time. MCC 35 pellets exhibited lowest modulus and hardness.     

Preparation and properties of water‐soluble chitosan and polyvinyl alcohol blend films as potential bone tissue engineering matrix

The blend film was prepared by casting solutions of water‐soluble hydroxyethyacryl‐chitosan (HEA‐CS) and polyvinyl alcohol (PVA) and cross‐linked by glutaraldehyde. The structure and properties of the blend films were estimated by wide‐angle X‐ray diffraction (WXRD), contact angle measurements with water, and scanning electron microscopy (SEM). The tensile properties of the blend films were investigated and the tensile strength (TS) and the elongation increased with the increased amount of PVA. The thermal stability (thermogravimetric (TG) and derivative thermogravimetric (DTG)) was evaluated and HEA‐CS was more thermally‐stable than that of PVA. The water swelling properties analysis indicated that HEA‐CS in the blends promoted the water absorption owing to its porous structure and the antimicrobial ability of the blend films was retained. Indirect cytotoxicity assessment of the blend films with human bone sarcoma cell (SW1353) indicated that the biomaterials were non‐toxic and did not release substances harmful to living cells. Copyright © 2009 John Wiley & Sons, Ltd.     

Effect of water on foaming properties of diglycerol fatty acid ester-oil systems

We have studied the effect of added water on the nonaqueous foaming properties of diglycerol fatty acid ester nonionic surfactant systems. Diglycerol monomyristate (designated as DGM) could not foam in nonpolar oils squalane and hexadecane at normal room temperature. Nevertheless, addition of a small amount of water induces a dramatic change in foaming properties. Both the foamability and foam stability increases with the amount of added water within the studied concentration range. Phase behavior study showed that in the dilute regions there is dispersion of solid surfactant in the aforementioned oils in the DGM systems. The particle size of the dispersed solid phase was found to be several tens of microns in the water free system, and hence it tends to coagulate and precipitate. In the case of shorter alkyl chain length, diglycerol monolaurate (DGL) surfactant-oil systems, dispersion of lamellar liquid crystal (Lalpha) is observed at room temperature, and the poor foaming properties were attributed to the large particle size of the liquid crystal. In both the DGL and DGM-oil systems, we observed a tendency of the particle size to decrease with the increasing concentration of added water. At higher temperature, the solid surfactant transforms to lamellar liquid crystal phase, and foaming is improved in the DGM/squalane system. Foams are stable for several minutes. Judging from the foaming test and particle size distribution data it can be concluded that the poor foaming in the diglycerol fatty acid esters-oil systems may possibly be due to bigger particle size, which causes precipitation. Addition of water results in the dispersion of smaller particles and improves the foaming behavior.     

氟橡胶/改性乙丙橡胶并用胶的热稳定性

采用热分析技术考察了氟橡胶及氟橡胶(FPM)/改性乙丙橡胶(MEPDM)并用胶在氮气中的热稳定性, 通过微分法与积分法两种动力学方法计算出了FPM及FPM/MEPDM并用胶的热分解活化能E和指前因子A. 结果表明, 并用胶的热分解温度稍高于纯的氟橡胶, 但热分解活化能略低于氟橡胶, FPM、FPM/MEPDM(5%)和FPM/MEPDM(10%)的热分解活化能分别为251.74、244.98和219.60 kJ·mol-1; 热分解反应级数n均为0.95. 随着失重百分率的增大, 热分解活化能增大.     

Thermal properties of polypropylene post-consumer waste (PP PCW)

Differential scanning calorimetry has been used to study the heat flow during melting and crystallisation of a range of polypropylene post-consumer waste (PP PCW) grades and blends. The heat flow curves and the heat capacity curves indicated that the PP PCW grades and blends contained contaminants even after manual sorting and a cleaning process. The enthalpies of the PP PCW grades were lower than that for the virgin grades, as a result of degradation. Small amounts of polymeric contaminants (up to 10%) did not affect the enthalpies of PP PCW although other contaminants may have had some effect. The enthalpies of the PCW blends could in general be predicted by a linear additive rule, which is of importance for recycling a variety of PP PCW products.The authors would like to thank Dr. M. Killen (Basell Australia Pty. Ltd.), Mr. P. Slaven (Citiwide MRF), Dasma Valley Waste Prop. Ltd. and Mr. I. Janetzki (Huhtamaki Australia Ltd.) for supplying materials for this project. Financial support for the project was provided by Basell Australia and Ecorecycle Victoria, Australia.     

Microcrystalline cellulose powders: structure, surface features and water sorption capability

Characterization of an Avicel PH 102 MCC powder through polymerization degree determination, Xray diffraction and N₂ adsorptions at subcritical temperatures is described. Specific characterizations of MCC/H₂O exchange in different environments were performed by means of thermogravimetric weight losses on time/temperature scale and analyses of water adsorption/absorption from saturated vapors at 310K. The reversibility of MCC/H₂O interactions and the influence of different surface area probes on the specific surface area are discussed.     

Characterisation of ground tyre rubber by using combination of FT-IR numerical parameter and DTG analysis to determine the composition of ternary rubber blend

Three different batches of ground tyre rubber (GTR), obtained from end of life (EOL) tyres, in the form of powder, were subjected to quantitative analysis using simple non-pyrolytic Fourier Transform Infrared (FT-IR) spectroscopy and derivative thermogravimetric (DTG) analysis. Two batches were based on EOL truck tyres varying in particle size, and one batch was based on EOL passenger car tyres. The focus was to derive a general method for finding multiple polymer blend compositions in different types of GTR for future efficient recycling applications of EOL tyres. The secondary aim was to evaluate the validity of the methodology independent of particle size. IR studies detected the presence of NR, SBR and BR characterized by peaks at 1375, 699 and 738 cm⁻¹, respectively, in all the batches. Each of the blends was ternary, in which the ratio of two rubbers was exactly calculated by combined use of an existing infrared blend parameter (P_IR) and the absorbance ratio of the characteristic peaks of the two rubbers in a baseline corrected IR spectrum. Then, using this calculated ratio on the results obtained from DTG, all three rubbers were quantified.     

Spin-lattice relaxation behaviour of water in cellulose materials in relation to the tablet forming ability of microcrystalline cellulose particles

Medical tablet forming ability of microcrystalline cellulose (MCC) was investigated in relation to the mobility of water molecules in MCC particles. For this purpose, the spin-lattice relaxation time T1 of water in the system was measured by 1H-NMR. Over a wide range of water contents (0.02 H2O/cellulose (g/g) 1.79), two different T1 (T1,l and T1,s) values were observed for water in each MCC sample. Below the equilibrium water content, water having these two different T1 values exchange with each other in an MCC particle reaching an equilibrium state within a given time scale (equilibrium constant K). The T1,l, T1,s and K values for water in MCC, estimated at the equilibrium water content, showed fairly good correlations with the hardness of the tablets made by the MCC samples. Sample with a shorter T1, or larger K tended to have a stronger tablet forming ability. In the spin-spin relaxation time T2 measurements for protons in an MCC/D2O system, two T2 components originating from the glassy cellulose solid (T2,G) and the swelling region (T2,l) were observed. It was found that the mole fraction xL of protons with T2,L in the system exhibits a clear linear correlation with K. From these results, a structural model for the distribution of water in MCC particles was propoed by taking the surface of each microfibril and the disordered region within the microfibril into consideration     

Characterization of heavy-metal-containing seepage water colloids by flow FFF, ultrafiltration, ELISA and AAS

Heavy-metal-containing humic colloids from seepage water samples of three different municipal waste disposal plants were characterized in terms of molecular weight, hydrodynamic radius and heavy metal content. The size distribution of the colloids was determined with ultrafiltration (UF) and flow field-flow fractionation (flow FFF). The humic colloids in the seepage water samples were characterized using an off-line coupling of flow FFF with an enzyme-linked immunosorbent assay (ELISA) for humic substances. The heavy metals in the different size fractions obtained by UF and flow FFF were determined using atomic absorption spectroscopy (AAS). The colloid size distributions obtained with UF showed a maximum of the distribution in the range 1–10 nm. Seepage water samples with high colloid concentrations had a second maximum in the range 0.1–1 m. The determination of colloid size with flow FFF gave different colloid size distributions for the three waste disposal seepage waters, whereas water from the oldest disposal plant showed the smallest colloid size with a maximum at 0.9 nm and water from the most recent plant showed the largest colloid size with a maximum at 1.3 nm. The determination of particle classes with regard to the chemical composition using a scanning electron microscope with energy dispersive X-ray fluorescence detector (SEM/EDX) showed that the particles can be divided into five classes: silicates, insoluble salts, iron(hydr)oxides, carbonates and organic colloids (humic colloids). Flow FFF/ELISA off-line coupling showed that the most frequently occurring colloids of the seepage waters were humic colloids and investigation of the UF-size-fractions with AAS showed that up to 77% of the total mass of a heavy metal element can be bound to particles, especially to humic colloids. Additionally, the distributions of the heavy metals Fe, Cu and Zn were investigated with flow FFF/AAS off-line coupling. These results also showed that a substantial amount of these heavy metals (up to 46%) was bound to humic colloids.     

Preparation and characterization of zwitterionic surfactant-modified montmorillonites

A series of zwitterionic surfactant-modified montmorillonites (ZSMMs) were synthesized using montmorillonite and three zwitterionic surfactants with different alkyl chain lengths at different concentrations [0.2-4.0 cation exchange capacity (CEC)]. These ZSMMs were characterized by X-ray diffraction (XRD), thermo-gravimetric analysis and differential thermo-gravimetric (TG/DTG) analyses. The zwitterionic surfactant could be intercalated into the interlayer spaces of montmorillonites and causing interlayer space-swelling. From XRD measurements, the amount of the surfactants loaded and the basal spacing increased with surfactant concentration and alkyl chain length. One endothermic DTG peak occurred at ~390 °C, which was assigned to the decomposition of the zwitterionic surfactant on the organo-montmorillonites from 0.2 to 0.6 CEC. When the surfactant loading was increased, a new endothermic peak appeared at ~340 °C. From the microstructures of these ZSMMs, the mechanism of zwitterionic surfactant adsorption was proposed. At relatively low loadings of the zwitterionic surfactant, most of surfactants enter the spacing by an ion-exchange mechanism and are adsorbed onto the interlayer cation sites. When the concentration of the zwitterionic surfactant exceeds the CEC of montmorillonite, the surfactant molecules then adhere to the surface-adsorbed surfactant. Some surfactants enter the interlayers, whereas the others are attached to the clay surface. When the concentration of surfactant increases further beyond 2.0 CEC, the surfactants may occupy the inter-particle space within the house-of-cards aggregate structure.     

The morphology of immiscible PDMS/PIB blends filled with silica nanoparticles under shear flow

The influence of surface nature (hydrophobic and hydrophilic) and concentration of silica nanoparticles on the coalescence behavior of immiscible polydimethylsiloxane (PDMS)/polyisobutylene (PIB) (90/10) blends under simple low-rate shear flow were investigated via optical shear technique. It was found that the coalescence of PIB droplets in PDMS matrix was suppressed efficiently by incorporating hydrophobic silica nanoparticles, and a constant droplet size was obtained at high particle contents. The addition of a small amount (<0.4 wt.%) of hydrophilic silica nanoparticles also decreased the size of PIB droplets. Clusters of small PIB droplets were formed at low filler concentration. When the filler concentration exceeded 0.8 wt.%, the clusters of PIB drops disappeared and elongated PIB threads with large size were formed, which suggest that the coalescence of PIB droplets was promoted. The results indicate that the discrepancy in the morphology evolution of PDMS/PIB blends upon the addition of silica nanoparticles is controlled not only by the surface chemistry of nanoparticles but also by their concentration in the blends.     

Experimental Study on Purification of Diesel Particulate Matter by Non-thermal Plasma Technology

In order to investigate the effects of non-thermal plasma (NTP) on diesel particulate matter (PM), an engine test bench was built up. An engine exhaust particle sizer (EEPS) was introduced to analyze the emission concentration and size distribution of PM and a thermo-gravimetric analyzer was used to analyze the effects of NTP on the composition of the particulate matter in the exhaust gas. The results show that the size distribution interval of the particle mass concentration falls behind that of the quantity concentration under various loads. When the diesel engine operating speed is 2400 rpm and the load is 25%, after NTP, the proportions of the nucleation mode particles and the accumulative mode particles exhibit a small fluctuation while the proportion of ultrafine particles decreases by 10% due to their large quantity concentration. Under the dual effect of DPF and NTP, the particle quantity concentration decreases by 98%. In order to investigate the effect of NTP on the composition of the PM, a thermo-gravimetric analysis of the particles obtained before and after NTP was carried out. The results show that the proportion of volatile matter falls by 16.05% and solid carbon accounts for an increase of 7.29%. NTP has the ability to improve reduction activity of particles and make particles easier to be oxidized at a lower temperature.