Influence of wood mercerization on the crystallization of polypropylene in wood/PP composites

Mercerization process is very significant because the alkali treatment facilitates reactivity of lignocellulosic fillers, thus allowing better response to chemical modification. In the present study, the effect of mercerization of pine wood on the nucleation ability of polypropylene was investigated by means of differential scanning calorimetry. We discovered that for the composites with wood containing cellulose II, the decrease in the crystal conversion of the polymer matrix and increase in the half-time of crystallization values are significant. It can be concluded that the amount of cellulose II formed upon alkalization of lignocellulosic fillers determines their nucleation ability. To evaluate the transcrystalline effects caused by various woods, which were untreated or treated with sodium hydroxide, the polarized optical microscopy was also performed. The nucleation of polypropylene on the surface of wood was investigated by induction time measurement. It was found that surfaces of the unmodified wood generate epitaxial nucleation, whereas the mercerized wood generates nonepitaxial nucleation. The differences in the type of nucleation suggest that the effectiveness of formation of transcrystalline structures depends on the contribution of cellulose I and cellulose II. Moreover, the presence of epitaxy is not necessary for the appearance of transcrystalline structures. The results showed that the transcrystalline structures appeared in each system, even with wood containing significant contribution of cellulose II. The only difference noted was the change in the nucleation abilities of the wood surface. Results of this study imply the necessity of quantitative determination of the contributions of cellulose I and cellulose II, whose presence determine the type of nucleation and nucleation ability of the filler surface.     

Tensile behaviour of isotactic polypropylene modified by specific nucleation and active fillers

Commercial-grade polypropylene was modified with a specific nucleation agent based on an amide of dicarboxylic acid, which promotes crystallization predominantly in the β-phase. The resulting material was used as a matrix for composites containing 10%, 20%, and 30% (by weight) of different calcium carbonate fillers. These fillers differed in particle size and surface treatment. The β-phase content, morphology and tensile mechanical properties were investigated. A distinct β-nucleation activity was found with surface-treated fillers; nevertheless, to obtain stiff and reasonably ductile composite materials, a matrix containing a critical nucleant concentration (0.03 wt%) was necessary.     

A study of transcrystallinity in polypropylene in the presence of wood irradiated with gamma rays

The interest in lignocellulosic composites has been growing in recent years because of their specific properties. In this study, a new technique of wood treatment using γ-irradiation was used. This research focuses on the influence of the gamma irradiation on the chemical composition of wood and on the nucleation ability of polypropylene matrice. The inner morphology of the transcrystalline layer was investigated using hot stage optical microscopy. Differential scanning calorimetry was used to investigate the kinetic parameters of polypropylene crystallization in the presence of wood surface. The results showed that the gamma irradiation can decrease the content of the cellulose in the wood, but it has a slightly negative effect on the transcrystallization process of polypropylene. This treatment also affects the crystal conversion and the half-time of PP crystallization. These results suggested that the gamma irradiation of wood may play a useful role in changing the microstructure of the matrice near the wood. It was observed that the nucleation of the wood surface was selective, indicating that the chemical characteristics of the lignocellulosics might have influence on the polypropylene crystallization. A possible mechanism for the appearance of transcrystallinity involving chemical composition of lignocellulosic is also proposed.     

Influence of Accelerated Weathering on the Properties of Polypropylene/Polylactic Acid/Eucalyptus Wood Composites

In the view of producing environmentally friendly materials without compromising properties, new composites containing polypropylene as a matrix and eucalyptus wood, with or without 15% of polylactic acid, were melt processed. In order to improve compatibility between components, a chemical modification of wood with toluene-2,4-diisocyanate (TDI) was realized and evidenced by changes in FT-IR and XPS spectra. The morphological, mechanical, and thermal characterizations of the obtained composites were evaluated before and after accelerating weathering. The results showed that the material comprising 15% TDI-modified wood, PP, and 15% PLA exhibited the best properties.     

表面改性氢氧化镁阻燃聚丙烯的研究进展

聚丙烯是综合性能良好的五大通用塑料之一,但是其易燃的特点限制了其在很多领域的应用。氢氧化镁(MH)作为一种环境友好型的无机阻燃剂,常被用于阻燃聚丙烯,但是未经改性的MH极性强,易团聚,与基体的相容性差,难以在聚合物基体中均匀分散,在导致阻燃效率低的同时,对复合材料的力学性能也有很大的负面影响,为提高MH在聚合物基体中的界面相容性,往往需要对MH进行表面改性。本文总结了近几年来以表面化学改性、表面接枝改性、微胶囊化改性三种方法改性的MH阻燃聚丙烯的研究进展,并对其下一步的研究方向进行了展望。     

The effect of crosslinking on mechanical properties of ldpe filled with organic fillers

Mechanical properties of low density polyethylene filled with various organic fillers were investigated. Different effect of different fillers on the properties was observed and the effect of crosslinking of these materials is also different. Fine anisotropic fillers behave similarly as inorganic fillers. The effect of crosslinking is the highest for composites containing large particulate fillers like beech wood flour. The effects are discussed in terms of mechanical behaviour and crosslinking degree determined from extraction or equilibrium swelling data. A formation of covalent bonds between the filler surface and polymeric matrix is proposed as a result of crosslinking.     

Polymer Composites with Plasma-Treated Fillers

A Large-volume Microwave Plasma (LMP) generator has been used to irradiate mica and ground-wood fibers in inert and active gas environments. Irradiated fillers were subsequently incorporated in a polypropylene matrix at solids levels of 10 and 20%. Calorimetrically measured heats of immersion showed that substantial changes in surface properties of fillers were effected by irradiation in ethylene, ammonia, and similar active gases. These surface changes are reflected In ultimate tensile and elongation properties of composites which show marked improvement over controls based on unirradiated fillers. Although no appreciable response in melt viscosity has been observed, surface treatment of fillers does seem to increase significantly melt elasticity of filled composites. The implications of improved performance motivate a more detailed study of the use potential of LMP in the fomulation of polymer composites.     

Dispersion evaluation of microcrystalline cellulose/cellulose nanofibril-filled polypropylene composites using thermogravimetric analysis

Microcrystalline cellulose-filled polypropylene (PP) composites and cellulose nanofiber-filled composites were prepared by melt blending. The compounded material was used to evaluate dispersion of cellulose fillers in the polypropylene matrix. Thermogravimetric analysis (TG) and mechanical testing were conducted on composites blended multiple times and the results were compared with single batch melt blended composites. The residual mass, tensile strength, and coefficient of variance values were used to evaluate dispersion of the microcrystalline cellulose fillers in the PP matrix. The potential of using TG to evaluate cellulose nanofiber-filled thermoplastic polymers was also investigated and it was found that the value and variability of residual mass after TG measurements can be a criterion for describing filler dispersion. A probabilistic approach is presented to evaluate the residual mass and tensile strength distribution, and the correlation between those two properties. Both the multiple melt blending and single batch composites manufactured with increased blending times showed improved filler dispersion in terms of variation and reliability of mechanical properties. The relationship between cellulose nanofiber loading and residual mass was in good agreement with the rule of mixtures. In this article, the authors propose to use a novel method for dispersion evaluation of natural fillers in a polymer matrix using TG residual mass analysis. This method can be used along with other techniques such as scanning electron microscope (SEM), transmission electron microscope (TEM), and X-ray diffraction (XRD) for filler dispersion evaluation in thermoplastic composites.     

PP-g-(MAH/St)和PP-g-MAH对聚丙烯/木粉复合材料性能的影响

在转矩流变仪中用熔融接枝法制备马来酸酐(MAH)和苯乙烯(St)接枝聚丙烯（PP）-PP-g-(MAH/St)和PP-g-MAH,将其作为聚丙烯/木粉复合材料的相容剂。 FTIR证实MAH和St单体与PP发生接枝反应。 用SEM和DSC等手段考察两种相容剂对PP/木粉复合材料微观形貌和结晶性能的影响,探索了各种PP/木粉复合材料加工和力学性能不同的内在原因。 SEM显示,PP-g-(MAH/St)改性木粉比PP-g-MAH改性木粉在PP基体中分散性更佳,木粉与PP的界面更加模糊,相容性进一步改善。 DSC结果表明,PP-g-(MAH/St)改性体系可增强木粉对PP的异相成核作用,提高结晶温度和结晶度。 复合材料的加工和力学性能测试结果表明,PP-g-(MAH/St)改性效果明显优于PP-g-MAH。 复合材料的熔体质量流动速率随相容剂用量的增加而逐步下降,PP-g-(MAH/St)改性体系拉伸强度和弯曲强度却逐步上升,并在相容剂用量为4.8 g/100 g PP时达到极值。 此时其拉伸强度达40.62 MPa,分别是未改性体系和PP-g-MAH改性体系的1.29和1.17倍;其弯曲强度达45.72 MPa,分别是未改性体系和PP-g-MAH改性体系的1.23和1.59倍;而无缺口冲击强度却在相容剂用量为3.6 g/100 g PP时达到极值13.35 kJ/m2,分别是未改性体系和PP-g-MAH改性体系的1.62倍和1.42倍。     

Analysis of the Dynamic Crystallisation of Isotactic Polypropylene/α-Nucleating Agent Systems by DSC

The nucleation efficiency of dibenzylidene sorbitol, methyldibenzylidene sorbitol and 1,2,3,4-bis- (3,4-dimethylbenzylidene) sorbitol in the crystallisation of the monoclinic phase of isotactic polypropylene has been evaluated by differential scanning calorimetry as a function of cooling rate and nucleation agent concentration. In order to analyse the nucleation activity of the additives, the self-nucleation process of the pure polypropylene has also been studied by thermal techniques. A large increment in the crystallisation temperatures has been obtained even for the lowest additive concentration, and the nucleating efficiencies are of the highest observed for α-nucleating agents in isotactic polypropylene. This revised version was published online in August 2006 with corrections to the Cover Date.     

聚丙烯/硫酸钡复合体系的界面相互作用与流变性质和结晶行为的关系

制备了一系列具有不同界面状态的聚丙烯 (PP) 硫酸钡 (BaSO4)复合体 .PP BaSO4的界面分别用硅烷、硬脂酸、马来酸酐接枝聚丙烯 (PP g MAH)改性 .研究表明 ,填充体系的熔体粘度和熔体弹性均高于基体 .以硅烷和PP g MAH进行界面改性后 ,PP BaSO4的界面相互作用加强 ,导致复合体系中的熔体粘度和熔体弹性进一步提高 ,同时BaSO4对PP的成核活性提高 .填料用硬脂酸处理后 ,硬脂酸能够在填料粒子表面上形成一个包覆层 ,使粒子与PP的亲和性改善 .同时该包覆层具有润滑作用 ,使得复合体系的熔体粘度和熔体弹性下降 ,并使得该体系中BaSO4的成核活性低于硅烷和处理的体系 .本文探讨了由复合体系的熔体粘度定量比较填充复合体系中聚合物 填料界面相互作用的方法 ,讨论了界面改性对复合体系流变性质和结晶行为影响的机理     

Perspectives of application of the molecular layer deposition technique for controlling operational properties of materials for shipbuilding

The results of investigations of surface modification of glass hollow microspheres are summarized. The regularities of the chemical molecular layering nanotechnology and its application for production of fillers and composite materials of low density with improved operational properties are discussed. Influence of chemical modification on thermal stability and combustibility of various polymer composites is investigated.     

Combined effects of clay modifications and compatibilizers on the formation and physical properties of melt‐mixed polypropylene/clay nanocomposites

The melt mixing technique was used to prepare various polypropylene (PP)‐based (nano)composites. Two commercial organoclays (denoted 20A and 30B) served as the fillers for the PP matrix, and two different maleated (so‐called) compatibilizers (denoted PP‐MA and SMA) were employed as the third component. The results from X‐ray diffraction (XRD) and transmission electron microscope (TEM) experiments revealed that 190 °C was an adequate temperature for preparing the nanocomposites. Nanocomposites were achieved only if specific pairs of organoclay and compatibilizer were simultaneously incorporated in the PP matrix. For example, PP/20A(5 wt %)/PP‐MA(10 wt %) and PP/30B(5 wt %)/SMA(5 wt %) composites exhibited nanoscaled dispersion of 20A or 30B in the PP matrix. Differential scanning calorimetry (DSC) results indicated that the organoclays served as nucleation agents for the PP matrix. Generally, their nucleation effectiveness increased with the addition of compatibilizers. The thermal stability enhancement of PP after adding 20A was confirmed with thermogravimetric analysis (TGA). The enhancement became more evident as a suitable compatibilizer was further added. However, for the 30B‐included composites, thermal stability enhancement was not evident. The dynamic mechanical properties (i.e., storage modulus and loss modulus) of PP increased as the nanocomposites were formed; the properties increment corresponded to the organoclay dispersion status in the matrix. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4139–4150, 2004     

Crystallisation of polypropylene matrix in composites filled with wooden parts of rapeseed straw

Nucleation ability of native and modified rapeseed straw during the polypropylene crystallization from the melt was investigated by the DSC method. Composites were made from isotactic polypropylene and lignocellulosic material using extrusion and injection moulding techniques. They were obtained using polypropylenes differing with respect to melt flow rates and different varieties of rapeseed straw. Chemical modification was carried out in two stages: through mercerisation and treatment with acetic acid anhydride. In the course of investigations, it was found that both native and modified rapeseed straw acted as an active nucleant of polypropylene crystallisation characterised by low values of MFR indices. It was found that for polypropylenes with high MFR values, the values of crystallization temperatures and crystallization half-time in composites were identical when compared with non-filled polymers. The investigations demonstrated that there were insignificant differences among composites containing straw from different varieties of rapeseed. The analysis of crystallization temperatures confirmed that rapeseed straw modification failed to change this parameter of the crystallization process. A similar tendency was observed in the case of changes of the half-time crystallization process. Moreover, the analysis of the crystallization temperature and crystallization half-time showed that the presence in composites of lignified rapeseed straw particles played an important role in the crystallization conditions.     

Radiation-induced modification of montmorillonite used as a filler in PP composite

In order to improve compatibility between inorganic fillers and polymeric matrix, montmorillonite (MMT) particles were modified with maleic anhydride (MA), then irradiated with electron beam, and finally were dispersed in polypropylene (PP). It was found that absorption of MA on the surface of layered clay results in the formation of salt-type bonding. Radiation treatment generates in the organic modifier stable carbon-centered radicals which, upon dispersion of activated particles in PP, induce filler-matrix linkages. Thus, such a process is another approach which has been shown to be an effective way in overcoming organophobic character of inorganic fillers in polymeric composites.     

Application of dsc to study crystallization kinetics of polypropylene containing fillers

The present work is concerned with the comparison of nucleating efficiency of various organic and inorganic fillers of isotactic polypropylene: talc, chalk, wood flour, nano clay particles, carbon black, chitosan in the form of powder of the same content equal to 5 mass%. The kinetics of isothermal crystallization of isotactic polypropylene in the composite systems was evaluated by using DSC. Avrami equation was applied to the results. Calculated K and n parameters depend on filler applied. The σσ_e surface free energies were also found. The best nucleating agent found here was talc and carbon black. The organic filler as a chitosan powder forms amorphous inclusions in the composites on which IPP molecules cannot be adsorbed. Their presence disturbs a macromolecular diffusion and delays crystallization process of IPP. This revised version was published online in July 2006 with corrections to the Cover Date.     

Influence of cellulose polymorphs on the polypropylene crystallization

Results of the hitherto research work on alkalisation of lignocellulosic materials have been much divergent. In view of the above, the subject of this study is mercerization of cellulose from pine wood. This choice of the subject permitted observation of transformation of cellulose I to cellulose II with no participation of other components of lignocellulosic materials. According to X-ray results, during mercerization the isolated cellulose was easily (completely) transformed into cellulose II variety, while the pine wood was converted more slowly to cellulose II polymorphs. Therefore, it could be concluded that the presence of lignin and hemicelluloses in wood prevented the transformation from cellulose I to II. The main objective of this research was to establish the effect of cellulose varieties on the nucleation ability of different fillers by using differential scanning calorimetry (DSC) and polarizing microscopy. The nucleating effect of the fillers occurs only in the presence of cellulose I variety. In contrast, the presence of cellulose II variety seems to practically eliminate the nucleating effect of the fillers. Moreover, nucleation of the mercerized wood (mixture of cellulose I and II) can be also observed, but this effect is not strong. It should be emphasised that as yet no correlation has been reported between the quantitative composition of cellulose polymorphic forms (appearing not only in wood, but in cellulose isolated from wood as well) and the nucleation ability of lignocellulosic fillers.     

Experimental and modeling analysis of mechanical-electrical behaviors of polypropylene composites filled with graphite and MWCNT fillers

The incorporation of carbon fillers can improve the thermal and electrical conductivities of polymer composites but will also have a significant effect on the flexural and tensile behavior. In this paper, two types of carbon fillers were added to polypropylene - carbon nanotubes and synthetic graphite. The influences of these filler materials on the tensile, flexural and fracture toughness characteristics were measured and the electrical conductivity of composites was also investigated. It was observed that the fillers lead to a remarkable increase in the flexural and tensile modulus of polypropylene composites. The maximum flexural and tensile strengths slightly increased with the addition of graphite, however, they were significantly increased in the case of carbon nanotubes because MWCNTs possess exceptional stiffness and strength and their length to diameter ratio is extremely high when compared with graphite. Electrical conductivity of polypropylene composites was evaluated. Noteworthy, composites based on synthetic graphite show a percolation process at one order of magnitude concentration higher than MWCNT filled polypropylene. Fracture toughness results open a wide range of applications for PP-MWCNT composites. Several prediction models were inspected in this research and it was concluded that inverse rule of mixtures model showed the most accurate predictions of the tensile modulus for composites made of polypropylene.     

Thermal analysis and crystallinity study of cellulose nanofibril-filled polypropylene composites

The isothermal and non-isothermal decompositions of cellulose nanofiber (CNF) and microfibrillated cellulose (MFC)-filled polypropylene (PP) composites were evaluated and compared with microcrystalline cellulose (MCC)-filled composites by means of thermogravimetric analysis (TG). X-ray diffraction was employed to evaluate crystallinity of the composites. The degree of maximum thermal degradation (ultimate DTG peak value) increased and thermal degradation onset temperature decreased as the cellulose content increased because the thermal stability of cellulose fillers is lower than that of neat PP, but the thermal degradation of the composite was hindered at higher temperature conditions because of the increased residual mass content of the cellulose nanofibril fillers compared to the matrix polymer. The isothermal residual mass of the cellulose nanofibril-filled PP composites under melt blending and injection molding temperatures was decreased marginally by incorporation of the cellulose reinforcement but still exhibited considerable isothermal stability. The raw materials and composites examined in this study were not affected by the manufacturing process temperatures utilized to produce the composites. The MCC decreased the composite crystallinity while the nano-sized cellulose (CNF and MFC) did not appear to have an effect on crystallinity.     

Analysis of the isothermal crystallization of polypropylene/wood flour composites

Isothermal crystallization and melting of isotactic polypropylene in binary polypropylene-wood flour composites has been studied by DSC, and the influence of an ethylene-methacrylic acid copolymer interfacial agent analyzed. Wood flour induces a slight nucleating effect, reducing the basal interfacial free energy of nucleation and increasing the overall crystallization rate. The interfacial agent generates a compatibilization phenomenon and an increase in the basal interfacial free energies with respect to the binary composites. In both binary and ternary systems the melting behaviour is a function of undercooling and is unaltered by the presence of either wood flour or the interfacial agent.