Effects of microparticles on isotactic polypropylene: Thermomechanical and thermal properties

Five types of melamine-formaldehyde microcapsules, that is, with shells of different compositions [melamine formaldehyde shell or a melamine formaldehyde-poly(hexamethylene adipate glycol) shell] and containing or not a flame retardant, diammonium hydrogen phosphate (DAHP), have been prepared by an in situ polymerization method and have been added to an isotactic polypropylene matrix (iPP) by melt blending at 5 wt %. Wide-angle X-ray diffraction and differential scanning calorimetry were employed to investigate the crystallization behavior of the prepared iPP/microparticles composites. The tensile properties and the thermal stability were also evaluated. It was stated that the morphology and the shape of the microparticles not only influence the crystallization behavior but also the thermomechanical properties of these composites. Thus, rougher microparticles act as a nucleating agent for the iPP, and in the presence of microparticles containing DAHP, the α- and the β-crystals are formed. Moreover, the presence of microparticles improves the thermal stability of the iPP. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2566–2576, 2008     

Influence of core materials on thermal properties of melamine-formaldehyde microcapsules

A series of melamine-formaldehyde microcapsules as an intrinsic intumescent system was prepared by an in situ polymerization. The structural and thermal properties of the resultant microcapsules were studied. The surface morphology and chemical structure of microcapsules were investigated using scanning electron microscope (SEM), and Fourier-transform infrared spectroscope (FT-IR), respectively. The thermal properties of samples were investigated by thermogravimetric analysis (TGA) and by differential scanning calorimetry (DSC). The results showed that the thermo-physical properties are strongly dependant on the nature core content and the synthesis conditions. From the thermal analysis, it was concluded that microcapsules containing di-ammonium hydrogen phosphate exhibits characteristics of an intumescent system during their thermal degradation and could be interpreted due to the interaction between phosphate and melamine.     

Effect of halogenless flame retardants on the thermal properties, flammability, and fire hazard of cross-linked EVM/NBR rubber blends

This paper presents the results of investigating the thermal stability, flammability, and fire hazard of cross-linked EVM/NBR blends unfilled and filled with halogenless flame-retardant compounds such as melamine cyanurate or magnesium hydroxide. The thermal analysis of the blends was carried out in the atmosphere of air. The activation energy of the composite destruction was determined by two non-isothermal methods: Flynn–Wall–Ozawa’s and Kissinger’s methods. The flammability of the composites obtained was determined by the method of oxygen index and on the basis of their combustion in air. The fire hazard of the vulcanizates investigated was determined with the use of a cone calorimeter and on the basis of toxicometric parameters W _LC50SM. The test results have shown that the flame retardants used increase the thermal stability of the cross-linked blends and decrease their flammability, and thereby allow one to obtain self-extinguishing or non-flammable polymeric materials. The cross-linked EVM/NBR blends filled with these flame-retardant compounds are characterized by good mechanical properties and reduced fire hazard.     

Structure and thermal stability of microencapsulated phase-change materials

A series of microcapsules containing n-octadecane with a urea-melamine-formaldehyde copolymer shell were synthesized by in-situ polymerization. The surface morphology, diameter, melting and crystallization properties, and thermal stability of the microcapsules were investigated by using FTIR, SEM, DSC, TGA and DTA. The diameters of the microcapsules are in the range of 0.2–5.6 m. The n-octadecane contents in the microcapsules are in the range of 65–78wt%. The mole ratio of urea-melamine has been found to have no effect on the melting temperature of the microcapsules. Two crystallization peaks on the DSC cooling curve have been observed. The thermal damage mechanisms are the liquefied n-octadecane leaking from the microcapsule and breakage of the shell due to the mismatch of thermal expansion of the core and shell materials at high temperatures. The thermal stability of materials can be enhanced up to 10 °C by the copolymerization of urea, melamine and formaldehyde in a mole ratio 0.2:0.8:3. The thermal stability of 160 °C heat-treated microcapsules containing 8.8% cyclohexane can be further enhanced up to approximately 37 °C.     

Thermo‐physical properties of polypropylene fibers containing a microencapsulated flame retardant

A microencapsulated flame retardant with a melamine‐formaldehyde shell was prepared by in situ polymerization, then incorporated into an iPP matrix with a coupling agent to manufacture multifilament yarns by melt spinning. The influence of the post‐treatment on the resulted microcapsules with an alcoholic solution was also studied. The spinnability of these formulations based on the interface characterization from contact angle measurements, tensile test and thermal characterizations was explored to determine the maximum draw ratio (DR) to apply. Finally, knitted fabrics were processed from multifilaments, and their flame‐retardant properties were evaluated by performing fire tests according to the FMVSS 302 and Din 4102 part B experiments. The different mechanical and thermal behaviors were discussed in terms of the influence of the DR and the post‐treatment applied on fibers during the spinning process and during the recovery of the microcapsules, respectively. The results showed that it was possible to obtain multifilament yarns with a DR of 4, but the best properties were obtained with a DR of 3 and for un‐treated microcapsules. Furthermore, the samples containing un‐treated microcapsules reach a B rating at the FMVSS test with a fast flame progression and a very low duration of burning. Copyright © 2012 John Wiley & Sons, Ltd.     

Double-layered co-microencapsulated ammonium polyphosphate and mesoporous MCM-41 in intumescent flame-retardant natural rubber composites

Double-layered co-microencapsulated ammonium polyphosphate (APP) and mesoporous MCM-41 (M(A&M)) were prepared using melamine–formaldehyde resin and zinc borate by in situ polymerization. The structure of the microcapsules was characterized by particle size analysis, Fourier-transform infrared spectroscopy, and scanning electron microscopy. Double-layered microencapsulation gave APP narrow particle size distribution. The flame-retardant and mechanical effects of M(A&M) in natural rubber (NR) were evaluated using the limiting oxygen index, UL 94 test, thermogravimetric analysis, and tensile test. Results indicated that the NR/M(A&M) composites had much better flame-retardant and mechanical properties than the NR/APP/MCM-41 composites. The limited oxygen index value of the NR/M(A&M) composite reached the maximum, and the UL-94 ratings were increased to V-0 when the ratio of APP to MCM-41 was 39:1 in microcapsule. The occurrence of a synergistic effect between MCM-41 and intumescent flame-retardant in the NR composites was proved. This investigation provided a promising formulation for flame-retardant NR composites.     

Thermal degradation mechanisms of aluminium phosphinate, melamine polyphosphate and zinc borate in poly(methyl methacrylate)

The aim of this study was to investigate the thermal degradability, and in particular, the thermal degradation mechanism of organophosphorus flame-retardant poly(methyl methacrylate) (PMMA). For this purpose thermogravimetry and direct pyrolysis mass spectrometry analyses were used. Release of diethylphosphinic acid, melamine, and several products involving Al-O-P and N-P linkages were detected from the organophosphorus additive containing aluminium diethylphosphinate, melamine polyphosphate and zinc borate. When incorporated in PMMA, reactions of diethylphosphinic acid, melamine and/or their derivatives with the ester group affected the decomposition pathways by generation of (C₂H₅)₂POOCH₃ and HNCO at relatively high temperatures.     

Effects of protective colloids on the preparation of poly(l-lactide)/poly(butylene succinate) microcapsules

Poly(l-lactide)/poly(butylene succinate) microcapsules containing an aqueous solution of sodium(+)-tartrate dihydrate were prepared by the interfacial precipitation method through solvent evaporation from (w/o)/w emulsion. The effects of poly(vinyl alcohol) used as a protective colloid in the microencapsulation were investigated regarding thermal properties, particle size distributions, surface morphologies, and release behaviors of the biodegradable microcapsules. It was concluded that encapsulation efficiency, surface morphologies, thermal properties, and releasing speed were closely related to the particle size distributions of microcapsules under different conditions of the protective colloid.     

Melamine,silica, and ionic liquid as a novel flame retardant for rigid polyurethane foams with enhanced flame retardancy and mechanical properties

Rigid polyurethane (PU) foams were successfully filled with different weight ratios of melamine (1 wt%, 5 wt%, 10 wt%), silica (0.1 wt%) and ionic liquid, 1-Ethyl-3-methylimidazolium chloride, [EMIM]Cl (0.3 wt%). The aim of this study was to improve the flame retardancy of PU foams and to develop the synergistic effect between melamine, silica and ionic liquid on the flame-retardant PU foams. The influence of different loadings of the fillers was examined. The results showed that in comparison with unfilled foam, all modified compositions are characterized by higher density (41–46 kg m⁻³), greater compression strength (134–148 kPa), and comparable thermal conductivity (0.023–0.026 W m⁻¹ K⁻¹). Moreover, the reaction to fire of the PU composites has been investigated by the cone calorimeter test. The results showed that the fire resistance of PU foams containing as little as 1 wt% of melamine is significantly improved. For example, the results from the cone calorimeter test showed that the incorporation of the melamine, silica and ionic liquid significantly reduced the peak of heat release rate (pHRR) by ca. 84% compared with that of unmodified PU foam. SEM results showed that incorporated fillers can form an intumescent char layer during combustion which improves the reaction to fire of the composite foams.     

Co-microencapsulate of ammonium polyphosphate and pentaerythritol in intumescent flame-retardant coatings

Co-microencapsulated ammonium polyphosphate (APP) and pentaerythritol (PER) [M (A&P)] is prepared using melamine–formaldehyde resin by in situ polymerization method and characterized using energy dispersive spectrometer and Fourier transform infrared spectra. Thermal stability and fire resistance behavior have been analyzed and compared. The co-microencapsulation of APP and PER leads to a great improvement of its thermal stability investigated by thermogravimetric analysis. The temperature of maximum mass loss rate of M (A&P) is 30 °C higher than that of APP/PER mixture. The flame-retardant effect of M (A&P) in coating composite is evaluated by carbonization volume, flame spread rate, and cone calorimeter. Results show that the flame-retardant properties of M (A&P) in coating composite is much better than that of APP/PER mixture coating composite.     

Optimization of parameters in preparation of PCM microcapsules based on melamine formaldehyde through dispersion polymerization

Microencapsulated phase change materials have attracted special attention due to their wide applications in saving and releasing energy. Here, microencapsulation of hexadecane (HD) in melamine formaldehyde shell was carried out through in situ dispersion polymerization in the aqueous media. Some important parameters such as stabilizer type and amount, surfactant amount, homogenization conditions as the critical affective factors on final particle size, morphology, and thermal resistance of the microcapsules were investigated extensively. The obtained microcapsules were concurrently analyzed by SEM, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA) techniques. SEM images showed that the best stabilization was achieved by polyvinyl alcohol. Also, particle size, as an indication of surface area for heat transfer properties, showed a decrement by increasing stabilizer amount, surfactant amount, and homogenization speed. The amount of entrapped HD and efficiencies of microencapsulation were determined by DSC, and the reason for observing such changes were discussed in detail. Thermal stability of the microcapsules as an important property for their performance was investigated, too. The results illustrated that an improved thermal stability would be obtained by an efficient stabilization in the emulsification step. Also the highest thermal stability up to 388 °C was reached at homogenization speed of 6,000 rpm. Finally, the optimized conditions for desirable encapsulation were proposed in such systems.     

3D-map modelling for the melting points prediction of intumescent flame-retardant coatings

The applicability of 3D map modelling for melting point prediction was studied. The melting points in the ammonium polyphosphate–pentaerythritol–melamine chemical system of intumescent flame-retardant coatings over a wide range of concentrations were collected. The ternary diagram (triangle) of the melting points was plotted and an approximated 3D map was built for the range 205–345°C. The present work contains the thermal data for the observed ternary system and provides a new graphic system for making predictions for intumescent flame-retardant coatings. The applicability of the calculated 3D map for obtaining experimental samples of fire-retardant paints with a low melting point for thin steel constructions was shown.     

Preparation of Polylactide Composite with Excellent Flame Retardance and Improved Mechanical Properties

Despite the good biodegradable and mechanical properties, poly(lactic acid) still suffers from a highly inherent flammability, which restricts its applications in the electric and automobile fields. In order to improve the flame retardancy of PLA, in this work, melamine polyphosphate (MPP) and zinc bisdiethylphosphinate (ZnPi) were firstly incorporated into PLA, and the synergistic effect of them on flame retardance of PLA was investigated using limiting oxygen index (LOI), UL-94 vertical measurement, scanning electron microscopy (SEM) and cone calorimeter tests etc. The results showed that PLA composite with 15 wt% of MPP/ZnPi (3:2) had the best flame-retardant efficiency with LOI value of 30.1 and V0 rating in UL-94 tests, which was far better than using MPP or ZnPi alone. What is more, although a wide range of flame retardants have been developed to reduce the flammability, so far, they normally compromise the mechanical properties of PLA. On the premise of maintaining good flame-retardant performance, we improved the toughness of flame-retardant PLA composite, and the impact strength of flame-retardant PLA composite was more than tripled (8.08 kJ/m²) by adding thermoplastic urethanes (TPU). This work offers an innovative method for the design of the unique integration of extraordinary flame retardancy and toughening reinforcement for PLA materials.     

正十六烷聚脲微胶囊化相变材料

用界面聚合法，合成了直径大约2.5 μm可用于热能储存含相变材料的聚脲包覆微胶囊.在含乳化剂的水溶液中，将溶有芯材正十六烷的有机相乳化成微米级油性液滴，随后加入的水溶性单体二胺与甲苯2,4-二异氰酸酯在胶束界面相互反应形成囊壁.分别用乙烯二胺，1,6-己二胺和它们的混合物作为水溶性单体进行了研究.并用红外光谱和热分析分别考察了不同胺类对微胶囊化学结构和热性质的影响.红外谱图显示合成了聚脲微胶囊，热重曲线表明含正十六烷的聚脲微胶囊能够耐受大约300 ℃高温，差示扫描量热测试表明所有样品均具有合适的相转变热，冷热循环实验揭示微胶囊能够维持储热容量不衰减.研究表明微胶囊化的正十六烷作为相变储热材料具有良好的应用前景.     

Influence of T31 content on combustion and thermal degradation behaviors on flame-retardant epoxy composites

To study the influence of the T31 content on the combustion properties and thermal degradation behaviors of flame-retardant epoxy composites, a series of flame-retardant epoxy composites were prepared using E-44 epoxy resin as matrix, T31 curing agent as curing agent, and intumescent flame retardant (IFR, based on phosphorus acid, melamine, and pentaerythritol) as flame retardant. The influence of T31 content on combustion behaviors and thermal degradation properties of the flame-retardant epoxy composites were studied using cone calorimeter test (CCT) and thermal-gravimetric analysis (TG), respectively. The cone calorimeter test results indicate that the decrease of T31 can significantly decrease the HRR, THR, SPR, and enhance the char residue of the epoxy composites. EP-4 with 7.0 wt% T31 shows the lowest HRR, SPR and the highest char residue. Furthermore, the TG results indicate that the EP-4 has the highest char residue among all the epoxy composites.     

Red phosphorus as a flame retardant for a thermoplastic nitrogen-containing polymer

Studies were made of the flame-retardant and smoke-suppressant activity of red phosphorus, in the presence of a brominated (decabromobiphenyl) and/or a nitrogenated (melamine) compound, on acrylonitrile-butadiene-styrene terpolymer. These studies were complemented by simultaneous thermal analyses of the polymeric systems. Red phosphorus is oxidised on heating and the thermal decomposition of any system containing this additive includes a substantial weight gain stage at ca 700 K. Melamine is volatilised very early on and thereafter acts only as a smoke suppressant in the gas phase. Decabromobiphenyl and red phosphorus interact positively in decreasing the flammability of the substrate, particularly at atomic ratios not lower than stoichiometric. The acrylonitrile content in ABS is very important, suggesting that the additives act mainly in the gas phase but that they also form some sort of charry layer on the polymer surface.     

A novel phase-change composites based on silicone rubber containing energy-storage microcapsules

A novel phase-change composites based on silicone rubber (MVQ) containing n-octadecane/poly (styrene-methyl methacrylate) microcapsules were successfully obtained by mixing energy-storage microcapsules into MVQ matrix using three preparation methods. The effect of microcapsules content on thermal property of the composites was investigated by thermogravimetric analysis. The mechanical properties of the composites prepared by three methods were also investigated. The morphology and thermal properties of the composites were characterized by scanning electron microscopy (SEM), differential scanning calorimetry, and thermal response. Thermal and mechanical properties of the composites were excellent when the microcapsules were added into room temperature vulcanized silicone rubber with 2 phr (per hundred rubber) content and cured at room temperature. The composites were proved to have good energy-storage performance with 67.6 J g^?1 enthalpy value.     

Synthesis and characterization of microencapsulated dicyclopentadiene with melamine–formaldehyde resins

Microcapsules containing healing agents have been used to develop the self-healing polymeric composites. These microcapsules must possess special properties such as appropriate strength and stability in surrounding medium. A new series of microcapsules containing dicyclopentadiene (DCPD) with melamine–formaldehyde (MF) resin as shell material were synthesized by in situ polymerization technology. These microcapsules may satisfy the requirements for self-healing polymeric composites. The chemical structure of microcapsule was identified by using Fourier transform infrared (FTIR) spectrometer. The morphology of microcapsule was observed by using optical microscope (OM) and scanning electron microscope. Size distribution and mean diameter of microcapsules were determined with OM. The thermal properties of microcapsules were investigated by using thermogravimetric analysis and differential scanning calorimetry. Additionally, the self-healing efficiency was evaluated. The results indicate that the poly(melamine–formaldehyde) (PMF) microcapsules containing DCPD have been synthesized successfully, and their mean diameters fall in the range of 65.2∼202.0 μm when the adjusting agitation rate varies from 150 to 500 rpm. Increasing the surfactant concentration can decrease the diameters of microcapsules. The prepared microcapsules are thermally stable up to 69 °C. The PMF microcapsules containing DCPD can be applied to polymeric composites to fabricate the self-healing composites.     

Thermal degradation of organophosphorus flame-retardant poly(methyl methacrylate) nanocomposites containing nanoclay and carbon nanotubes

Filler nanoparticles pave the way for the development of novel halogen-free flame-retardant polymers. The aim of this study was to investigate the thermal degradability, and in particular, the thermal degradation mechanism of organophosphorus flame-retardant poly(methyl methacrylate) (PMMA) nanocomposites containing nanoclay (NC) and multi-walled carbon nanotubes (CNT). For this purpose, thermogravimetry and direct pyrolysis mass spectrometry analysis were utilized. The onset of degradation was delayed through increased maximum degradation temperature and suppressed mass loss corresponding to initial degradation stage with carbon nanotubes and nanoclays, respectively. Possibility of reactions of melamine and/or melamine derivatives and interactions between carbonyl groups of PMMA and phosphinic acid leading to thermally more stable products was increased owing to the barrier effect of filler nanoparticles. In the presence of NC better flame retarding characteristics was detected as anhydride formation, leading to charring being more effective.     

Intumescent flame retardation of polypropylene/bamboo fiber semi-biocomposites

Polypropylene/bamboo fiber (BFP) semi-biocomposites were prepared by melted blend method. Microencapsulated ammonium polyphosphate was added to the BFP semi-biocomposites to improve the flame-retardant properties of the BFP semi-biocomposites. The flame-retardant properties of the BFP semi-biocomposites have been investigated by limited oxygen index, UL-94 test and cone calorimeter test. The results of cone calorimeter show that the peak of heat release rate (pHRR) and total heat release (THR) of the flame-retardant BFP semi-biocomposites decrease substantially compared with that without MCAPP. The pHRR value of flame-retardant BFP semi-biocomposite decreases from 540.0 to 227.5 kW m^?2, and the THR value decreases from 75.3 to 49.2 MJ m^?2. The thermal degradation and gas products of the flame-retardant BFP semi-biocomposites were monitored by thermogravimetric analysis and thermogravimetric analysis-infrared spectrometry.