Differential scanning calorimetry of copolymer of isotactic polypropylene backbone with grafted poly(ethylene‐co‐propylene) branches

A series of graft polymers having polypropylene (PP) backbone and poly(ethylene‐co‐propylene) (EPR) side chains was prepared. PP backbone molecular weight (M_n) was 28–98 kg/mol, EPR side chain M_n was 2.6–17 kg/mol, and EPR content was 0–16 wt %. In this work, thermal analysis of the copolymers was performed using differential scanning calorimetry (DSC). Nonisothermal crystallization was performed at different cooling rates. The DSC thermograms revealed multiple melting peaks for slowly cooled samples, most likely the result of the melting of thinner tangential lamellae followed by the melting of thicker radial lamellae. Equilibrium melting temperature (T_m⁰) was determined using the linear Hoffman–Weeks method. Another approach was also used for determining T_m⁰: melting temperature (T_m) and crystallization temperature (T_c) were plotted as functions of logarithmic cooling rate. Linear relationships were observed for all samples with the cross points as T_m⁰'s. As cooling rate decreased, T_c, T_m, and enthalpy of fusion (ΔH_f) increased. T_m and T_m⁰ increased with increasing PP M_n. T_c and T_m were unaffected by the grafting of EPR onto the PP backbone. T_m⁰ and ΔH_f decreased as EPR content increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3380–3388, 2006     

Isothermal crystallization study on aqueous solution of poly(vinyl methyl ether) by DSC method

A study on the isothermal crystallization of water in aqueous solutions of poly(vinyl methyl ether) (PVME) was carried out by the differential scanning calorimetry (DSC). The influence of PVME concentration (49.5, 44.5 and 39.5 v%) and the crystallization temperature (T_c) on crystallization rate G, crystallization enthalpy (ΔH_c) and melting enthalpy (ΔH_m) was investigated. Avrami equation cannot be used to describe the crystallization process of water in aqueous PVME solution. Within the measured temperature range, the crystallization rate G increases with the crystallization temperature T_c and with the decreasing PVME content. The crystallization enthalpy ΔH_c linearly increases with the degree of supercooling. The influence of T_c on the ΔH_c becomes more marked with increasing PVME concentration. For 49.5 and 44.5 v% PVME solutions, the amount of water arrested in solution during the isothermal crystallization and the final concentration of PVME-rich phase increase linearly with the T_c, whereas for 39.5 v% PVME solution, these two values almost do not change with T_c. The amount of frozen water in the subsequent cold crystallization is approximately proportional to the initial T_c. The approximately constant ΔH_m for a given concentration at the different initial isothermal crystallization temperatures suggests that the total amount of ice from the first isothermal crystallization and the second cold crystallization is same. The quantitative relation of the amount of frozen water in the cold crystallization and the initial T_c demonstrates that PVME/water complexes are thermodynamically unstable.     

Nonisothermal crystallization of metallocene propylene–decene‐1 copolymers

The nonisothermal crystallization behavior of one metallocene‐based isotactic polypropylene and three propylene–decene‐1 copolymers was studied. The effects of comonomer content and cooling rate were investigated. It was found that comonomer units enchained systematically reduce the crystallization temperature (T_c), melting temperature (T_m), fusion enthalpy (ΔH_f), and crystallinity (X_c). Such an effect becomes more evident at a faster cooling rate. With increasing comonomer content, the supercooling required for crystallization increases and the overall crystallization rate is reduced. The Avrami equation is applicable to describe the nonisothermal crystallization kinetics of propylene–decene‐1 copolymer. It was shown that, although the reduced crystallization rate constant Z_c increases with comonomer content, the Avrami exponent decreases with comonomer content and cooling rate, leading to the smaller overall crystallization rate and larger crystallization half‐time of the copolymer with higher comonomer content. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1724–1730, 2004     

Crystallization and melting characteristics of metallocene isotactic polypropylenes

The measurement of crystallization and melting behaviors under constant rates of cooling and heating and the Avrami's analysis of isothermal crystallization were carried out for various metallocene‐ (MET‐PP) and Ziegler‐ Natta‐catalyzed (ZN‐PP) random polypropylene copolymers with various ethylene contents. Both the melting point T_m and the crystallization temperature T_c decrease with increasing ethylene content. Compared at the same ethylene content, both are lower for MET‐ PP because of the higher uniformities of stereoirregular bonds and copolymerization bonds. T_m and T_c show a linear correlation, and compared at the same T_c, T_m of MET‐PP is lower than that of ZN‐PP. This is because MET‐PP has narrower distributions of isotactic sequence length and hence of lamellar thickness than ZN‐PP. The heat of fusion and the latent heat of crystallization decrease with ethylene content. At the same ethylene content, both are lower for MET‐PP, owing also to the higher uniformities of stereoirregular bonds and copolymerization bonds. From the Avrami's analysis, it is assumed that there is little difference in crystallization modes of both catalyst PPs. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1851–1857, 2002     

Synthesis and characterization of poly(L‐lactide‐co‐ϵ‐caprolactone)‐b‐poly(L‐lactide) biodegradable diblock copolyesters: Effect of the block lengths on their thermal properties

Poly(L ‐lactide‐co‐ε‐caprolactone)‐b‐poly(L ‐lactide) [P(LL‐co‐CL)‐b‐PLL] diblock copolyesters were synthesized in a two‐step process with 1‐dodecanol (DDC) and stannous octoate as the initiating system. In the first‐step reaction, a 50:50 mol % amorphous poly(L ‐lactide‐co‐ε‐caprolactone) [P(LL‐co‐CL)] copolyester was synthesized via the bulk copolymerization of L ‐lactide and ε‐caprolactone, which was followed by the polymerization of the PLL crystalline block at the end chain in the second‐step reaction. The yielded copolyesters were characterized with dilute‐solution viscometry, gel permeation chromatography, ¹H‐ and ¹³C‐NMR, and differential scanning calorimetry methods. The molecular weights of the P(LL‐co‐CL) copolyesters from the first‐step reaction were controlled by the DDC concentrations, whereas in the second‐step reaction, the molecular weights of the P(LL‐co‐CL)‐b‐PLL diblock copolyesters depended on the starting P(LL‐co‐CL) copolyester molecular weights and L ‐lactide/prepolymer molar ratios. The starting P(LL‐co‐CL) copolyester molecular weights and PLL block lengths seemed to be the main factors affecting specific thermal properties, including the melting temperature (T_m), heat of melting (ΔH_m), crystallizing temperature (T_c), and heat of crystallizing (ΔH_c), of the final P(LL‐co‐CL)‐b‐PLL diblock copolyester products. T_m, ΔH_m, T_c, and ΔH_c increased when the PLL block lengths increased. However, these thermal properties of the diblock copolyesters also decreased when the P(LL‐co‐CL) block lengths increased. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Isothermal crystallization behavior of metallocene‐catalyzed isotactic polypropylene

Isothermal crystallization behavior of isotactic polypropylene (iPP) synthesized using metallocene catalyst was investigated in this work. The isotacticity of the polypropylene was characterized by ¹³C‐NMR spectroscopy. It was found that the melting temperature (T_m) of the iPP is 123.51°C and the crystallization temperature (T_c) is 93°C. The iPP synthesized in this work did not show a general increase of T_m with an increase of crystallization temperature T_c, due to the short crystallization time of 20 min and low molecular weight (number average molecular weight = 6,300). The iPP showed a tendency of increasing heat of fusion (ΔH_f) with decreasing crystallization temperature. All the spherulites of iPP samples showed negative birefringence. For the iPP sample crystallized at the highest T_c (= 123°C, just below T_m), the spherulite showed a pronounced Maltese Cross and a continuous sheaf‐like texture aligning radially, which suggests that R‐lamellaes are dominant in this spherulite. The crystalline structure of the iPP was also investigated by X‐ray diffraction. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 231–237, 2005     

Carbon black‐filled poly(ethylene‐co‐alkyl acrylate) composites: Calorimetric studies

The calorimetric characteristics of carbon black (CB)/poly(ethylene‐co‐alkyl acrylate) composites depend on both the CB and acrylate contents. An increase of the acrylate content in the pure copolymers tends to decrease all the crystalline characteristics: T_c,n, the nonisothermal crystallization temperature; T_m, the melting temperature, and ΔH_m, the melting enthalpy. CB modifies the crystallization kinetics of poly(ethylene‐co‐ethyl acrylate) (EEA) alone and in blends with poly(ethylene‐co‐24% w/w methyl acrylate) (24EMA) and poly(ethylene‐co‐35% w/w methyl acrylate) (35EMA). In the presence of CB, T_c,n, the nonisothermal crystallization temperature of EEA, increases and t_1/2, the half‐crystallization time, decreases for a given isothermal crystallization temperature, T_c,i. The thermograms obtained during the melting of EEA after isothermal crystallization show multiple endotherms, suggesting that crystalline‐phase segregation has occurred. The existence of different crystalline species can be explained by the presence of fractions of different acrylate content in the copolymers as shown by SEC. Therefore, CB does not seem to have much effect on the subsequent melting temperature of EEA, T_m,s. CB also induces a lower melting enthalpy, Δ H_m, in the blends. This decrease of ΔH_m appears to be constant whatever the compound, but when reported to the melting enthalpy of the polymer without CB, δΔH_m/ΔH_m increases with the acrylate content. A slight increase of the amorphous phase stiffness after CB introduction is noticed: The T_g of EEA/24EMA and EEA/35EMA blends increases by several degrees. Therefore, plotting ΔH_m versus ΔC_p shows that for the same ΔH_m the ΔC_p is lower in CB‐filled samples, suggesting there is some kind of rigid amorphous phase not contributing to the glass transition. We propose to explain the CB activity during the crystallization process by the existence of molecular interactions between CB and acrylate groups rather than by a pure nucleating effect. Thus, the increase of T_c,n and the decrease of ΔH_m could be explained by the fact that CB separates acrylate‐rich chains from the crystallization medium, accelerating the crystallization of the acrylate‐poor chains. During such a crystallization process, CB may be preferentially localized in the more polar amorphous phase and scattered between the two crystalline phases of EEA and EXA. These blends of poly(ethylene‐co‐alkyl acrylate) copolymers with CB provide interesting materials with adjustable properties depending on the acrylate and CB contents and on the thermomechanical treatments. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 779–793, 2001     

Effects of rosin‐type nucleating agent and low density polyethylene on the crystallization process of polypropylene

In this article, the influence of rosin‐type nucleating agent (Nu–Na) and low density polyethylene (LDPE) on the crystallization process of polypropylene (PP) from the melt state was studied by differential scanning calorimeter and polarization microscope. It was found that LDPE obstructed the crystallization of PP, decreased the crystallization rate of PP. The rosin‐type nucleating agent Nu–Na substantially improved the rate of crystallization, and decreased the size of spherulites also. The cooperative effect of LDPE and Nu–Na made the crystallization rate of PP increase greatly, the spherulites of PP became much smaller and dispersed more uniformly, and the transparency of PP was further improved evidently. The crystallization temperature (T_c) and melting temperature (T_m) of PP and LDPE in PP/LDPE/Nu–Na (97:3:0.5) were not affected by the number of mixed passes—the nuclei migration from PP to PE had not happened in the mixed passes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2804–2809, 2003     

Crystallization behavior and melting characteristics of PP nucleated by a novel supported β-nucleating agent

The β-nucleated PP with high β-PP content was prepared by a novel supported β-nucleating agent, which was prepared with pimelic acid supported on nano-CaCO₃ as support. The influences of the content of the support and supported β-nucleating agent, pre-melting temperature (T_melt) and scan rates on crystallization behavior and melting characteristics, and the β-PP content of β-nucleated PP were determined by Differential Scanning Calorimeter (DSC) and Wide-Angle X-ray Diffraction (WAXD). The results indicated that the addition of supported β-nucleating agent markedly increased the crystallization temperature (T_c) of PP. Increasing the content of supported β-nucleating agent slightly increased the T_c, but had no influence on the melting temperatures (T_m) of β-nucleated PP. The T_c and T_m of β-nucleated PP decreased slightly with increasing the content of the support nano-CaCO₃. The effects of scan rates and multiple scans with different T_melt on the crystallization and melting behavior of PP nucleated by supported β-nucleating agent are similar to that of PP nucleated by calcium pimelate (CaHA). The β-PP content above 90 percent was obtained in PP nucleated by supported β-nucleating agent and was not influenced by the content of nano-CaCO₃. The supported β-nucleating agent prepared by supporting pimelic acid on nano-CaCO₃ is a β-nucleating agent with high efficiency and selectivity, and low cost.     

Crystallization behavior of glass bead‐filled low‐density polyethylene composites

The effects of the filler content and the filler size on the crystallization and melting behavior of glass bead‐filled low‐density polyethylene (LDPE) composites have been studied by means of a differential scanning calorimeter (DSC). It is found that the values of melting enthalpy (ΔH_c) and degree of crystallinity (x_c) of the composites increase nonlinearly with increasing the volume fraction of glass beads, ϕ_f, when ϕ_f is greater than 5%; the crystallization temperatures (T_c) and the melting temperatures (T_m) of the composites are slightly higher than those of the pure LDPE; the effects of glass bead size on x_c, T_c, and T_m are insignificant at lower filler content; but the x_c for the LDPE filled with smaller glass beads is obviously greater than that of the filled system with bigger ones at higher ϕ_f. It suggests that small particles are more beneficial to increase in crystallinity of the composites than big ones, especially at higher filler content. In addition, the influence of the filler surface pretreated with a silane coupling agent on the crystallization behavior are not too outstanding at lower inclusion concentration. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 687–692, 1999     

Study of thermomechanical,structural and antibacterial properties of poly(lactic acid) reinforced with graphene oxide nanoparticles via melt mixing

Addition of graphene oxide (GO) to poly(l ‐lactic acid) (PLLA) offers an alternative approach for tuning its crystallinity, improving its mechanical properties and transfusing an antibacterial behavior. GO/PLLA nanocomposites were prepared by melt extrusion, thus avoiding the potentially toxic, for biomedical applications, residue of organic solvents. Fourier transform infrared spectroscopy verified the formation of intermolecular hydrogen bonds. Using differential scanning calorimetry experiments concerning the isothermal crystallization of PLLA and PLLA containing 0.4 wt% GO, a two‐dimensional disc‐like geometry of crystal growth was determined, whereas at 125 and 130 °C the nanocomposite developed three‐dimensional spherulitic growth. Higher crystallization rate constant values suggest that the incorporation of 0.4 wt% GO accelerated the crystallization of PLLA. The lowest crystallization half‐time for PLLA was observed at 115 °C, while at 110 °C GO caused its highest decrease, accompanied by the highest increase in melting enthalpy (ΔH_m), as compared to that of PLLA, after completion of isothermal crystallization. Their ΔH_m values increased with T_ic, whereas multiple melting peaks transited to a single one with increasing T_ic. GO improved the PLLA thermal stability, tensile strength and Young's modulus. Incorporation of 0.8 wt% GO endowed PLLA with another potential application as a biomaterial since the derived composite presented good thermomechanical properties and effective prohibition of Escherichia coli bacteria attachment and proliferation. This effect was more prominent under simulated sunlight exposure than in the dark. The preparation method did not compromise the intrinsic properties of GO. © 2020 Society of Chemical Industry     

Hybrid‐filler filled polypropylene/(natural rubber) composites: Effects of natural weathering on mechanical and thermal properties and morphology

Comparison was made between the properties of recycled newspaper (RNP)/carbon black (CB) and recycled newspaper (RNP)/silica hybrid filled polypropylene (PP)/natural rubber (NR) composites. The properties studied were mechanical, thermal, and morphological. These composites were also subjected to natural weathering, i.e., the tropical climate in Penang, Malaysia, for 6 months. The incorporation of CB and silica at all weight ratios of RNP/CB and RNP/silica hybrid gave increases in tensile strength, elongation at break (E_B), Young's modulus, melting temperature (T_m), heat of fusion of composites (ΔH_f(com)), crystallinity of composites (X_com), and the crystallinity of PP (X_PP). As expected, the tensile properties (except for Young's modulus), T_m, ΔH_f(com), X_com, and X_PP of the composites exhibited lower values after weathering than before weathering. The extent of chemical degradation was studied by Fourier transform infrared spectroscopy, and the results showed the formation of several functional groups, i.e., hydroxyl, hydroperoxide, vinyl, carboxylic acid, and ketone. At the same filler weight ratio, the composites filled with RNP/CB hybrid showed higher values of tensile strength and E_B but lower values of Young's modulus, ΔH_f(com), X_PP, and X_PP, as compared to those with the RNP/silica hybrid under weathering conditions. The good retention in tensile properties indicated that the replacement of RNP by CB and silica improved the weatherability performance of the PP/NR composites. J. VINYL ADDIT. TECHNOL., 2008. © 2008 Society of Plastics Engineers     

Sulfur‐containing polymers: Effect of composition on melting behavior and crystallization kinetics of poly(butylene terephthalate)

The melting behavior and crystallization kinetics of poly(butylene terephthalate/thiodipropionate) (PBT) copolymers were investigated using the differential scanning calorimetry technique. Multiple endotherms typical of PBT were observed in the copolymers under investigation and were found to be influenced both by crystallization temperature (T_c) and composition. Wide‐angle X‐ray diffraction measurements permitted the identification of the crystalline structure of PBT in all the copolymers investigated. By applying the Hoffman–Weeks method, the equilibrium melting temperature of the copolymers was derived. Isothermal crystallization kinetics were analyzed according to Avrami's treatment. Values of the exponent n close to 3 were obtained, independent of T_c and composition, results in agreement with it being a crystallization process originating from predetermined nuclei and characterized by three‐dimensional spherulitic growth. The introduction of butylene thiodipropionate units was found to decrease the PBT crystallization rate. The heat of fusion (ΔH_m) was correlated to the specific heat increment (Δc_p) of samples of different degrees of crystallinity, and the results were interpreted based on there being an interphase, whose amount was found to increase as the sulfur‐containing unit content was increased. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2003–2009, 2003     

Thermal analysis of ethylene–propylene copolymer-grafted-glycidyl methacrylate

The thermal properties of ethylene–propylene copolymer grafted with glycidyl methacrylate (EP-g-GMA) were investigated by using differential scanning calorimetry (DSC). Compared to the plain ethylene–propylene copolymer (EP), peak values of melting temperature (T_m) of the propylene sequences in the grafted EP changed a little, crystallization temperature (T_c) increased about 8–12°C, and melting enthalpy (ΔH_m) increased about 4–6 J/g. The isothermal and nonisothermal crystallization kinetics of grafted and ungrafted samples was carried out by DSC. Within the scope of the researched crystallization temperature, the Avrami exponent (n) of ungrafted sample is 1.6–1.8, and those of grafted samples are all above 2. The crystallization rates of propylene sequence in EP-g-GMA were faster than that in the plain EP and increased with increasing of grafted monomer content. It might be attributed to the results of rapid nucleation rate. © 1996 John Wiley & Sons, Inc.     

Melting behavior of poly(l-lactic acid): Effects of crystallization temperature and time

Effects of crystallization temperature and time on the melting behavior of poly(l-lactic acid) were studied with differential scanning calorimetry (DSC). The isothermal crystallization was performed at various temperatures (T_cs), and DSC melting curves for the isothermally crystallized samples were obtained at 10 K min⁻¹. When T_c was lower than T_d (∼135 °C), the double melting peaks appeared. The melting behavior, especially T_c dependence of the melting temperature (T_m), discretely changed at T_b (=113 °C), in accordance with the discrete change of the crystallization behavior at T_b, which was previously reported. When T_c was higher than T_d, a single melting peak appeared. In addition, T_c dependence of dT_m/dT_c discretely changed at T_d. That is, the melting behavior, especially T_c dependence of T_m and dT_m/dT_c, are different in three temperature regions of T_c divided by T_b and T_d: Regions I (T_c ≤ T_b), II (T_b ≤ T_c ≤ T_d), and III (T_d ≤ T_c). The effect of crystallization time on the melting behavior, melting temperature and heat of fusion in each temperature region of T_c is also discussed.     

Effects of silver nanoparticles on the dynamic crystallization and physical properties of syndiotactic polypropylene

The effects of silver (Ag) nanoparticles on the physical properties of syndiotactic PP (sPP) were investigated concentrating on the isothermal melt crystallization behavior under shear. sPP with 5 wt % Ag nanoparticles presented higher crystallization temperature (T_c) and heat of crystallization (ΔH_c) than pure sPP. At 90°C, the Ag nanoparticles had little effect on the induction time of crystallization but a little increased the half‐time (t_1/2) for the crystallization. At 100°C, however, the induction time was decreased with increasing the Ag content and the t_1/2 was decreased up to the Ag content of 0.5 wt %. DSC melting endotherms exhibited double melting peaks when crystallized at 90°C under shear but a single melting peak when crystallized at 100°C. The WAXD patterns exhibited that the presence of Ag nanoparticles did not produce any change in the crystal structure of sPP. The tensile strength of sPP is little changed up to the Ag content of 0.1 wt % but it was decreased with further addition. In addition, the introduction of less than 0.1 wt % Ag increased the elongation at break, but further addition decreased it abruptly. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of polyesteramide based hot melt adhesive obtained with dimer acid,castor oil and ethylenediamine

Polyesteramide based hot melt adhesives were synthesized from high purity dimer acid (composition: ~1% trimer acid, ~98% dimer acid and ~1% linoleic acid), ethylenediamine and castor oil. The effect of castor oil content on the properties of the hot melts, such as thermal properties: glass transition temperature (T_g), melting temperature (T_m), enthalpy of melting (H_m), crystallization temperature (T_c), enthalpy of crystallization (H_c) and softening point (T_s); mechanical properties: tensile strength, elongation at break and Shore D hardness; adhesion properties: lap shear strength (LSS) and T-Peel strength (TPS); and rheological properties were investigated. Ethylenediamine was replaced by 5%, 10% and 15% (molar basis) of castor oil. It was found that T_g, T_m, H_m, T_c, H_c, T_s, LSS, TPS, tensile strength, Shore D hardness and viscosity, all decreased with increased concentration of castor oil. This is due to the decrease in the crystallinity of the polyesteramide caused by conversion of amide linkages by ester linkages and increased distance between two ester linkages (due to the bulky nature of castor oil).     

Nonisothermal Crystallization and Melting Behavior of EVA/OMWNTs Nanocomposites

EVA/OMWNTs nanocomposites have been successfully prepared by a simple melt compounding method. The nonisothermal crystallization behaviors of the EVA/OMWNTs nanocomposites are strongly dependent on the degree of crystallinity (X_c), peak crystallization temperature (T_p), half-time of crystallization (t_1/2), and Avrami exponent (n) on the OMWNTs content and cooling rate. The dependence of the crystallization activity energy on the extent of relative crystallization for the plain EVA and the EVA/OMWNTs nanocomposites shows that ΔE increases with the increase in the relative degree of crystallinity below about 5%, and the ΔE decreased when the relative degree of crystallinity was greater than about 5%.     

Polypropylene/natural rubber composites filled with recycled newspaper: Effect of chemical treatment using maleic anhydride‐grafted polypropylene and 3‐aminopropyltriethoxysilane

A study on effect of chemical treatment using maleic anhydride‐grafted polypropylene (MAPP) and 3‐aminopropyltiethoxysilane (3‐APE) was investigated. The performance of the MAPP and 3‐APE were investigated by means of torque development, mechanical properties, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), scanning electron microscopy morphology, and water absorption. The results revealed that the use of MAPP or 3‐APE in the composites has increased the stabilization torque, tensile strength, Young's modulus, water absorption, and thermal stability of the PP/NR composites. The incorporation of MAPP in the composites shows higher stabilization torque, tensile strength, E_B, Young's modulus, and lower water uptake when compared with the use of 3‐APE in the PP/NR composites. TGA and DSC results indicated that primary and secondary peak of DTG curve, initial degradation temperature (T₀), degradation temperature (T_deg), melting temperature (T_m), heat of fusion of composites (ΔH_f(com)), crystallinity of composites (X_PP), and PP (X_PP) increased, while total weight loss and thermal degradation rate decreased for both treated composites. The MAPP‐treated RNP‐filled PP/NR composites were found to be more thermal resistance and more crystalline than 3‐APE‐treated filled PP/NR RNP composites. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers