Effects of nano‐TiO2 on the properties and structures of starch/poly(ε‐caprolactone) composites

Poor physical properties resulting from low interfacial interactions between hydrophilic biopolymers and hydrophobic thermoplastic matrices have been one of the biggest obstacles in preparing quality biomass materials. This study concentrates on the effects of nano‐TiO₂ on the properties and structure of starch/poly (ε‐caprolactone) (PCL) composites. The molecular and crystal structures of the composites were characterized by using Fourier transform infrared spectroscopy, differential scanning calorimeter (DSC), X‐ray diffraction (XRD), and field emission scanning electron microscope. The results indicated that an interpenetrating network structure formed by adding nano‐TiO₂ into starch/PCL composites. The DSC and XRD analysis indicated that the crystallinity degree and the crystallization rate of the composites reduced, whereas the crystal form and crystal size were unchanged. The results also showed that the mechanical properties and water resistance of the composites were improved significantly with the addition of nano‐TiO₂, whereas their transparency decreased. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4129–4136, 2013     

Solid‐state synthesis and characterization of polyaniline/nano‐TiO2 composite

Polyaniline/nano‐TiO₂ composites with the content of nano‐TiO₂ varying from 6.2 wt % to 24.1 wt % were prepared by using solid‐state synthesis method at room temperature. The structure and morphology of the composites were characterized by the Fourier transform infrared (FTIR) spectra, ultraviolet‐visible (UV–vis) absorption spectra, X‐ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The electrochemical performances of the composites were investigated by galvanostatic charge–discharge measurement, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The results from FTIR and UV–vis spectra showed that the composites displayed higher oxidation and doping degree than pure PANI. The XRD and morphological studies revealed that the inclusion of nano‐TiO₂ particles hampered the crystallization of PANI chains in composites, and the composites exhibited mixed particles from free PANI particles and the nano‐TiO₂ entrapped PANI particles. The galvanostatic charge–discharge measurements indicated that the PANI/nano‐TiO₂ composites had higher specific capacitances than PANI. The composite with 6.2 wt % TiO₂ had the highest specific capacitance among the composites. The further electrochemical tests on the composite electrode with 6.2 wt % TiO₂ showed that the composite displayed an ideal capacitive behavior and good rate ability. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Study on the properties of nano‐TiO2/polybutylene succinate composites prepared by vane extruder

Different proportions of nanoscale TiO₂ (nano‐TiO₂)‐filled polybutylene succinate (PBS) composites were prepared by vane extruder. The crystalline, thermal, dynamic viscoelastic, mechanical, and UV‐resistance properties of the composites were studied, and X‐ray diffraction, differential scanning calorimetry, and thermogravimetric analysis were conducted. Results show that the crystalline structure of the PBS composites did not change with TiO₂ addition. TiO₂ almost has no effect on the crystallization and melting behavior of PBS. Nevertheless, the introduction of TiO₂ has improved the thermal stability, tensile modulus, flexural modulus, and flexural strength of the PBS composites. The UV resistance of the composites has also been significantly enhanced with TiO₂ addition. POLYM. COMPOS., 35:53–59, 2014. © 2013 Society of Plastics Engineers     

Effect of in situ surface‐modified nano‐SiO2 on the thermal and mechanical properties and crystallization behavior of nylon 1010

Nylon 1010 composites filled with two types of surface‐modified SiO₂ nanoparticles (RNS and DNS) were prepared by melt blending. The mechanical properties of the composites were evaluated. The influences of the surface‐modified nano‐SiO₂ on the thermal stability, crystallization behavior, and microstructure of nylon 1010 were investigated by thermogravimetric analysis, differential scanning calorimetry (DSC), X‐ray diffraction, and transmission electron microscopy. And the interfacial interactions between the fillers and polymer matrix were examined using a Fourier transformation infrared spectrometer. It was found that the addition of the surface‐modified nano‐SiO₂ had distinct influences on the thermal stability, mechanical properties, and crystallization behavior of nylon 1010. RNS and DNS as the fillers had different effects on the mechanical properties of nylon 1010. The composites filled with RNS at a mass fraction of 1–5% showed increased break elongation, Young's modulus, and impact strength but almost unchanged or even slightly lowered tensile strength than the unfilled matrix. The DNS‐filled nylon 1010 composites had obviously decreased tensile strength, whereas the incorporation of DNS also contributed to the increase in the Young's modulus of nylon 1010, but less effective than RNS. Moreover, the nylon 1010 composites had better thermal stability than the neat polymer matrix, and the composites filled with RNS were more thermally stable than those filled with DNS. The difference in the crystallinity of neat nylon 1010 and its composites filled with RNS and DNS was subtle, although the surface‐modified nano‐SiO₂ could induce or/and stabilize the γ‐crystalline formation of nylon 1010. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Crystallization of glass fiber‐reinforced poly(p‐phenylene sulfide) nanocomposites

Ternary composites of glass fiber‐reinforced poly(p‐phenylene sulfide) (PPS/GF) filled with nanometric calcium carbonate (nano‐CaCO₃) were prepared by means of a twin‐screw extruder. The nano‐CaCO₃ surface was treated with stearate and treated with titanate, the composites being called SI composite system and SII composite system, respectively. The crystallization and heatproof properties of the PPS/GF/nano‐CaCO₃ composites were measured using a differential scanning calorimeter, to investigate the influence of the nanometric filler content on the crystallinity. The results show that the variation of the starting crystallization temperature, crystallization temperature and crystallinity with an increase of the particle weigh fraction (?_f) of SI composite system is different from that of SII composite system. When ?_f is less than 4 wt%, the crystallinity of the two composite systems increases and then decreases slightly with increasing ?_f. Moreover, the crystallization behavior and mechanisms are discussed. Copyright © 2011 Society of Chemical Industry     

Crystallization kinetics of polypropylene composites filled with nano calcium carbonate modified with maleic anhydride

The subject of this study was the crystallization behavior and thermal properties of polypropylene (PP)/maleic anhydride (MAH) modified nano calcium carbonate (nano‐CaCO₃) composites. In this study, 5 wt % nano‐CaCO₃ modified with different contents of MAH was filled into a PP matrix. X‐ray diffraction and differential scanning calorimetry were used to characterize the crystal morphology and crystallization kinetics of a series of composites. The results demonstrate that the nano‐CaCO₃ modified with MAH had an important effect on the thermal and morphological properties of the nanocomposites. The Avrami exponent of the pure PP was an integer, but those of the composites were not integers, but the crystallization rate constant decreased as the content of MAH in the nano‐CaCO₃ filler increased in isothermal crystallization. In nonisothermal crystallization, the kinetic parameter F(T) and the degree of crystallinity of pure PP were compared with those of the PP composites filled with nano‐CaCO₃. We suggest that heterogeneous nucleation existed in the PP composites and that the transformation and retention of the β‐form crystal into the α‐form crystal took place in the composite system and the β‐form crystal had a higher nucleation rate and growth process than the α‐form crystal in the PP composites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation of nano poly(phenylsilsesquioxane) spheres(nano‐PPSQ) and study of the thermal stability and crystallization behavior of PP/nano‐PPSQ composites

The preparation of nano poly(phenylsilsesquioxane) particles (nano‐PPSQ) and the influence of nano‐PPSQ on the thermal stability and crystallization of polypropylene (PP) were studied. The morphology and thermal stability of PP/nano‐PPSQ composites were characterized by scanning electron microscopy (SEM) and the thermogravimetric analysis (TGA). The SEM result showed that the particles were well dispersed in the PP matrix. The TGA results of the PP/nano‐PPSQ composites indicated that the incorporation of nano‐PPSQ can improve the thermal stability of PP. The crystallization behavior and kinetics of PP/nano‐PPSQ composite were studied by X‐ray diffraction (XRD) and differential scanning calorimetry (DSC). The XRD revealed that the addition of nano‐PPSQ influences the crystallinity and crystal size of PP. The Avrami, Ozawa, and combined Avrami/Ozawa (Mo method) equations were applied to describe the crystallization kinetics and estimate the kinetic parameters of mathematical models under the nonisothermal crystallization of PP and PP/nano‐PPSQ composites. The results show that nano‐PPSQ influences the crystallization temperature and rate. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis,physical properties,and characterization of starch‐based blend films by adding nano‐sized TiO2/poly(methyl metacrylate‐co‐acrylamide)

The purpose of this study was to improve the physical properties and to expand the application range of starch‐based blend films added nano‐sized TiO₂/poly(methyl methacrylate‐co‐acrylamide) (PMMA‐co‐AM). Starch‐based blend films were prepared by using corn starch, polyvinyl alcohol (PVA), nano‐sized PMMA‐co‐AM, nano‐sized TiO₂/PMMA‐co‐AM particles, and additives, i.e., glycerol (GL) and citric acid (CA). Nano‐sized PMMA‐co‐AM was synthesized by emulsion polymerization and TiO₂ nanoparticles were also prepared by using sol–gel method. Nano‐sized TiO₂/PMMA‐co‐AM particles were synthesized by wet milling for 48 h. The morphology and crystallinity of TiO₂, nano‐sized PMMA‐co‐AM and TiO₂/PMMA‐co‐AM particles were investigated by using the scanning electron microscope (SEM) and X‐ray diffractometer (XRD). In addition, the functional groups of the TiO₂/PMMA‐co‐AM particles were characterized by IR spectrophotometry (FTIR). The physical properties such as tensile strength (TS), elongation at break (%E), degree of swelling (DS), and solubility (S) of starch‐based films were evaluated. It was found that the adding of nano‐sized particles can greatly improve the physical properties of the prepared films. The photocatalytic degradability of starch/PVA/nano‐sized TiO₂/PMMA‐co‐AM composite films was evaluated using methylene blue (MB) and acetaldehyde (ATA) as photodegradation target under UV and visible light. The degree of decomposition (C/C₀) of MB and ATA for the films containing TiO₂ and CA was 0.506 and 0.088 under UV light irradiation and 0.586 (MB) and 0.631 (ATA) under visible light irradiation, respectively. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Isothermal crystallization kinetics and melting behaviors of nanocomposites of poly(trimethylene terephthalate) filled with nano‐CaCO3

The isothermal crystallization and subsequent melting behavior of poly(trimethylene terephthalate) (PTT) composites filled with nano‐CaCO₃ were investigated at designated temperatures with differential scanning calorimetry. The Avrami equation was used to fit the isothermal crystallization. The Avrami exponents were determined to be 2–3 for the neat PTT and PTT/CaCO₃ composites. The particles of nano‐CaCO₃, acting as nucleating agents in the composites, accelerated the crystallization rate, with the half‐time of crystallization decreasing or the growth rate constant (involving both nucleation and growth rate parameters) increasing. The crystallization activation energy calculated from the Arrhenius formula was reduced as the nano‐CaCO₃ content increased from 0 to 2%, and this suggested that nano‐CaCO₃ made the molecular chains of PTT easier to crystallize during the isothermal crystallization process. Subsequent melting scans of the isothermally crystallized composites exhibited triple or double melting endotherms: the greater the content was of nano‐CaCO₃, the lower the temperature was of the melting peak. The degree of crystallization deduced from the melt enthalpy of composites with the proper concentration of nano‐CaCO₃ was higher than that of pure PTT, but it was lower when the nano‐CaCO₃ concentration was more than 2%. The transmission electron microscopy pictures suggested that the dispersion state of nano‐CaCO₃ particles in the polymer matrix was even when its concentration was no more than 2%, whereas some agglomeration occurred when its concentration was 4%. Polarized microscopy pictures showed that much smaller or less perfect crystals formed in the composites because of the interaction between the molecular chains and nano‐CaCO₃ particles. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Anionic nylon 6/TiO2 composite materials: Effects of TiO2 filler on the thermal and mechanical behavior of the composites

The nylon 6‐based composite materials containing untreated and surface‐treated TiO₂ particles with 3‐aminopropyltriethoxysilane (APTEOS), as coupling agent were prepared by in situ anionic polymerization of ε‐caprolactam in the presence TiO₂ as a filler using the rotational molding technique. The thermal behavior and mechanical properties of the neat nylon 6 and its composites were investigated using various techniques such as differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), a tensile and flexural test and impact strength. Experimental results revealed that both untreated and surface‐modified TiO₂ had distinct influence on the melting temperature (T_m), crystallization temperature (T_c), and degree of crystallinity (α_DSC), thermal stability, storage modulus (E′), and loss factor (tan δ), and mechanical properties of nylon 6 matrix. Dynamical mechanical analysis indicated that addition of TiO₂ particles into nylon 6 matrix increased both the storage modulus and the glass transition temperature. The corresponding values of nylon 6 composites with modified filler were higher than that of nylon 6 composite with untreated TiO₂ particles. Tensile and flexural characteristics of the nylon 6 composites were found to increase while the elongation at break and impact strength with increase in TiO₂ concentration relative to neat nylon 6. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Biodegradable poly(L‐lactic acid)/TiO2 nanocomposites: Thermal properties and degradation

Poly(L ‐lactic acid)‐titanium dioxide nanocomposites (with various loadings of TiO₂: 0.5, 1, 2, 5, and 10 wt %) were produced by solution casting method. The influence of TiO₂ on thermal properties and crystallinity of PLA was investigated by DSC and FTIR spectroscopy. The TiO₂ nano filler has no significant influence on the characteristic temperatures (T_g, T_c, and T_m), but has high impact on the crystallinity of these systems. The degree of crystallinity X_c significantly increases for PLA nanocomposites loaded with up to 5 wt % of TiO₂, while for 10 wt % load of TiO₂ it drops below X_c of the pure resin. The degradation of the prepared composites was evaluated hydrolytically in 1N NaOH, enzymatically in α‐amylase solutions, and under UV irradiation. The catalytic effect of TiO₂ nano particles on the degradation processes under UV light exposure (λ = 365 nm) and hydrolytic degradation was confirmed with the increase of the filler content. The opposite effect was identified in enzymatic degradation experiments. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of calcination temperature of TiO2 on the crystallinity and the permittivity of PVDF‐TrFE/TiO2 composites

Composite membranes of poly(vinylidene‐trifluoroethylene)/titanium dioxide (PVDF‐TrFE/TiO₂) were prepared by the solution cast method. The crystallization behavior and dielectric properties of the composites with TiO₂ calcined at different temperatures were studied. Transmission electron microscopy and X‐ray diffraction (XRD) results showed that the TiO₂ nanoparticles calcined at different temperatures were well dispersed in the polymer matrix and did not affect the structure of the PVDF‐TrFE matrix. XRD and differential scanning calorimeter measurements showed that the crystallinity of PVDF‐TrFE/TiO₂ composites increased as the addition of TiO₂ with different calcination temperatures. The dielectric property testing showed that the permittivity of PVDF‐TrFE/TiO₂ membrane increased rapidly with the increase of TiO₂ content and the calcination temperature of TiO₂ at constant TiO₂ content, but the dielectric loss did not change much. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Tribological properties of micro‐ and nanoparticles‐filled poly(etherimide) composites

It has been found that nano‐ or microsized inorganic particles in general enhance the tribological properties of polymer materials. In the present study, 5 vol % nano‐TiO₂ or micro‐CaSiO₃ was introduced into a polyetherimide (PEI) matrix composite, which was filled additionally with short carbon fibers (SCF) and graphite flakes. The influence of these inorganic particles on the sliding behavior was investigated with a pin‐on‐disc testing rig at room temperature and 150°C. Experimental results showed that both particles could reduce the wear rate and the frictional coefficient (μ) of the PEI composites under the applied testing conditions. At room temperature, the microparticles‐filled composites exhibited a lower wear rate and μ, while the nano‐TiO₂‐filled composites possessed the lowest wear rate and μ at elevated temperature. Enhancement in tribological properties with the addition of the nano‐particles was attributed to the formation of transfer layers on both sliding surfaces together with the reinforcing effect. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1678–1686, 2006     

Effects of ball milling dispersion of nano‐SiOx particles on impact strength and crystallization behavior of nano‐SiOx–poly(phenylene sulfide) nanocomposites

Ball milling and mixing with strong shear force and strike force were applied to get fine dispersion of nano‐SiO_x particles in poly(phenylene sulfide) (PPS) powder. Nano‐SiO_x/PPS composites were manufactured by intensive compounding with 3 wt% nano‐SiO_x particles. Effects of the ball milling dispersion on crystal behavior and impact strength of nano‐SiO_x/PPS nanocomposites were studied. Physical mechanisms of ball milling dispersion were investigated. Evaluations based on both WAXD and DSC indicates that crystallization behavior of nano‐SiO_x/heat‐treated PPS (HT‐PPS) nanocomposites was influenced by the ball milling process. Their crystallinity was 25% less while Izod impact strength was 89% better than those of as‐received neat PPS. Increased kinetic energy via ball milling by external work makes nano‐SiO_x able to overcome the attraction from itself to prevent agglomeration. Interfacial bonding of two phases between nano‐SiO_x and PPS was enhanced by crosslinking in HT‐PPS and reduction in surface tension of interface during ball milling. The bonds allow SiO_x to dissipate energy and thus improve PPS impact strength from the addition of nano‐SiO_x. POLYM. ENG. SCI., 46:820–825, 2006. © 2006 Society of Plastics Engineers     

Effects of nano‐tio2 on the performance of high‐amylose starch based antibacterial films

The purpose of this article is to investigate the effects of nano‐tianium dioxide (nano‐TiO₂) on the high‐amylose starch/polyvingl alcohol (PVA) blend films prepared by a solution casting method. The results show that at the concentration of 0.6% of nano‐TiO₂, the film demonstrated the best tensile strength at 9.53 MPa, and the elongation at break was noted as 49.50%. The optical transmittance of the film was decreased and the water resistance was improved with further increase of the concentration of nano‐TiO₂. Using the techniques of Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and field‐emission scanning electron microscopy (SEM), the molecular and the crystal structures of the films were characterized. The results indicate that the miscibility and compatibility between high‐amylose starch and PVA were increased with the addition of nano‐TiO₂ into the films due to the formation of hydrogen and C? O? Ti bonds. The antimicrobial activities of the blend films were also explored. The results show that there were inhibitory zones around the circular film disc, which is attributable to the addition of nano‐TiO₂. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42339.     

Polyethylene‐Palygorskite nanocomposite prepared via in situ coordinated polymerization

A polyethylene/palygorskite nano‐composite (IPC composite) was prepared via an in‐situ coordinated polymerization method, using TiCl₄ supported on palygorskite fibers as catalyst and alkyl aluminum as co‐catalyst. These composites were compared with those prepared by melt blending (MBC composites). It was found that in the IPC composites, nano‐size fibers of palygorskite were uniformly dispersed in the polyethylene matrix. In contrast, in the MBC composites, the palygorskite was dispersed as large clusters of fibers. Regarding the mechanical properties of the IPCs, the tensile modulus increased and the elongation at break decreased with increasing fiber content, while the tensile strength passed through a maximum. The tensile strength and elongation at break were much smaller for the MBC composites. The final degree of crystallinity of the IPC composites decreased with increasing palygorskite content. Regarding the kinetics of crystallization, the ratio between the degree of crystallinity at a given time and the final one was a universal function of time. It was found that large amouns of gel were present in the IPC composites and much smaller amountes in the MBC composites.     

Effect of particle size and surface modification on mechanical properties of poly(para‐dioxanone)/inorganic particles

Poly(para‐dioxanone) (PPDO)‐based composites have been prepared by blending PPDO with three different types of CaCO₃ particles, CC1 (nano‐CaCO₃), CC2 (CaCO₃ whisker), and CC3 (silane‐coated CaCO₃ whisker). The effects of particles size, interface adhesion, and crystallinity of composites on mechanical properties were discovered through analysis of the morphology of fracture surfaces, thermal characteristics, and crystalline structure. DSC revealed that the CaCO₃ particles acted as a nucleating agent and promoted crystallinity of PPDO. The effect of CaCO₃ particles on crystallization of PPDO was clearly revealed by using the nucleating efficiency. Smaller size particles exhibit greater nucleating efficiency. Adhesion between PPDO and the CaCO₃ particles plays major roles on the mechanical properties of composites. The tensile strength of PPDO was improved over 54%. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

The crystallization,thermal and mechanical properties of nano‐Sb2O3 filled poly(butylene terephthalate)

Nano‐Sb₂O₃ particles were modified by a combination modifier of cetyltrimethyl ammonium bromide (CTAB) and KH‐560 via the mechanochemical method based on high‐energy ball milling. Then, the testing specimens of the nano‐Sb₂O₃/PBT composites of differing compositions were prepared by melting blending technology. The crystallization, thermal, and mechanical properties of composites were characterized by X‐ray diffraction, differential scanning calorimetry, thermogravimetric analyzer, and mechanical performance test. The tensile and impact fracture surfaces of composites were determined by scanning electron microscopy. Besides, the influence of the Sb₂O₃ nanoparticles surface modification on crystallinity, mechanical properties of the composites, and the interfacial adhesion between nano‐Sb₂O₃ and PBT was systematically investigated. The results indicate that the main crystalline characteristics of PBT matrix remain unchanged in the nanocomposites. However, the addition of nano‐Sb₂O₃ particles plays a heterogeneous nucleation and can effectively improve the crystallization of PBT matrix. In addition, the compound modification of the nano‐Sb₂O₃ can effectively enhance mechanical properties of the composites and interfacial interaction between nano‐Sb₂O₃ and PBT. The enhanced fracture properties in the nanocomposites were caused by the assisted void formation at the edge of the nano‐Sb₂O₃ particle. When the nano‐Sb₂O₃ mass fraction is 3%, the composites show excellent comprehensive performance. The interfacial adhesion parameter B and the half‐debonding angle θ of composites were assessed to quantitatively characterize the interfacial adhesion strength between nano‐Sb₂O₃ and PBT. Finally, the reinforcement and toughening mechanisms were described. J. VINYL ADDIT. TECHNOL., 26:268–281, 2020. © 2019 Society of Plastics Engineers     

Nonisothermal crystallization behavior and crystals morphology of poly(trimethylene terephthalate)/nano‐calcium carbonate composites

Nonisothermal crystallization behavior and crystal morphology of poly(trimethylene terephthalate) (PTT) composites filled with modified nano‐calcium carbonate (CaCO₃) had been investigated by using differential scanning calorimetry and polarized optical microscopy. The modified Avrami equation and Ozawa theory were used to investigate the nonisothermal crystallization, respectively. The particles of nano‐CaCO₃, acting as a nucleation agent in composites, accelerated the crystallization rate by decreasing the half‐time of crystallization or increasing the parameters of Z_c and K(T). Moreover, the nano‐composite with 2 wt% nano‐CaCO₃ exhibited the highest crystallization rate. The Avrami and the Ozawa exponents, n and m of the nano‐composites, were higher than those of neat PTT, suggesting more complicated interaction between molecular chains and the nanoparticles that cause the changes of the nucleation mode and the crystal growth dimension. The effective activation energy calculated from the Friedman formula was reduced as nano‐CaCO₃ content increased, suggesting that the nano‐CaCO₃ made the molecular chains of PTT easier to crystallize during the nonisothermal crystallization process. The optical micrographs showed that much smaller or less perfect crystals were formed in composites because of the presence of the nano‐CaCO₃ particles. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Crystallization and melting behavior of nano‐CaCO3/polypropylene composites modified by acrylic acid

Nano‐CaCO₃/polypropylene (PP) composites modified with polypropylene grafted with acrylic acid (PP‐g‐AA) or acrylic acid with and without dicumyl peroxide (DCP) were prepared by a twin‐screw extruder. The crystallization and melting behavior of PP in the composites were investigated by DSC. The experimental results showed that the crystallization temperature of PP in the composites increased with increasing nano‐CaCO₃ content. Addition of PP‐g‐AA further increased the crystallization temperatures of PP in the composites. It is suggested that PP‐g‐AA could improve the nucleation effect of nano‐CaCO₃. However, the improvement in the nucleation effect of nano‐CaCO₃ would be saturated when the PP‐g‐AA content of 5 phf (parts per hundred based on weight of filler) was used. The increase in the crystallization temperature of PP was observed by adding AA into the composites and the crystallization temperature of the composites increased with increasing AA content. It is suggested that the AA reacted with nano‐CaCO₃ and the formation of Ca(AA)₂ promoted the nucleation of PP. In the presence of DCP, the increment of the AA content had no significant influence on the crystallization temperature of PP in the composites. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2443–2453, 2004