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Nonisothermal Crystallization of High Density Polyethylene and Nanoscale Calcium Carbonate Composites

Jiann-Wen Huang,1 Ya-Lan Wen,2 Chiun-Chia Kang,3 Wei-Jen Tseng,4 Mou-Yung Yeh4,5 1 Department of Styling and Cosmetology, Tainan University of Technology, Taiwan, Republic of China

Department of Nursing, Meiho Institute of Technology, Neipu Hsiang, Taiwan, Republic of China R&D Center, Hi-End Polymer Film Co., Ltd., Taiwan Department of Chemistry, National Cheng Kung University, Taiwan, Republic of China Sustainable Environment Research Centre, National Cheng Kung University, Taiwan, Republic of China




Nonisothermal crystallization of high density polyethylene (HDPE)/maleic anhydride-modified HDPE(manPE)/ nanoscale calcium carbonate (CaCO3) nanocomposite was investigated by means of wide angle X-ray diffraction (WAXD), polarized optical microscopy (POM), and differential scanning calorimetry (DSC). WAXD indicated that the crystallinity was reduced with the addition of CaCO3. The spherulite size of HDPE increased in the presence of manPE, but decreased when CaCO3 was added from observation of POM. A modified Avrami analysis, Ozawa analysis, and Liu analysis were applied to the nonisothermal crystallization process. Crystallizability followed the order: HDPE/manPE/ CaCO3 > HDPE/CaCO3 > HDPE/manPE > HDPE when undercooling was taken into account. Dependence of the effective activation energy on the relative crystallinity was estimated by the Friedman equation, and the results were used to calculate the parameters (Kg and U*) of Lauritzen-Hoffman’s equation by Vyazovkin’s method. These results indicate that the addition of maleic anhydride groups and CaCO3 tend to promote the nucleation of spherulites on their surfaces and lead to epitaxial growth of the crystallites. But at the same time, manPE and CaCO3 particles may hinder the transport of the molecule chains resulting in a decrease of the crystallization growth rate. POLYM. ENG.
SCI., 48:1268–1278, 2008. ª 2008 Society of Plastics Engineers

INTRODUCTION Polymer nanocomposites containing inorganic fillers have attracted great attention because of their significant improvements in mechanical strength and thermal properties at low filler loadings [1–3]. They have combined the advantages of the matrix polymer and the unique characteristics of metal nanoparticles. Inorganic particles are widely used as reinforcing agents, such as calcium carbonate (CaCO3) and silica (SiO2). High density polyethylene (HDPE) is a semicrystalline polymer and one of the most widely used commodity polymers for domestic and industrial applications. The compatibility of HDPE with other materials is very poor because HDPE does not contain any polar groups in its backbone. The introduction of polar functional groups, such as maleic anhydride, to the HDPE matrix could increase the polarity and improve the compatibility with other materials [4–6]. Some nanocomposites based on polyethylene (PE) have been studied by researchers, such as lower density PE/copper [7], HDPE/montmorillonite [8], and HDPE/vermiculite [1]. Results from these studies demonstrated that the addition of nanoscale fillers influence not only the mechanical properties but also the crystallization. The dispersed nanoscale fillers may act as a heterogeneous nucleation agent to enhance the crystallization rate of the PE matrix [1, 8], and the fillers, at the same time, may also hinder the transport of the molecule chains to reduce crystallization growth rate [7]. In our previous works [9], nanoscale CaCO3 particles were dispersed in HDPE with maleic anhydride-grafted

Correspondence to: J.W. Huang; e-mail: DOI 10.1002/pen.21087 Published online in Wiley InterScience ( C V 2008 Society of Plastics Engineers

and 36. the nonisothermal crystallization of neat HDPE. As a base of comparison. and then cooled to 298 K at a cooling rate of 10 K/min. China. although undercooling is an important factor in crystallization rate. Nonisothermal Crystallization The nonisothermal crystallization behaviors of polymer blends were investigated with a differential scanning calorimeter (DSC). 20 wt% manPE. held for 5 min at the temperature. RESULTS AND DISCUSSION WAXD Figure 1 shows the X-ray diffraction patterns of HDPE and HDPE blends which were cooled from the melt state at a cooling rate of 10 K/min. As listed in Table 1. polarized optical microscope (POM). The CaCO3 particles are dispersed well in HDPE/manPE/ CaCO3 blend.16 kgf. and Trade Name: NPCC-201). only a few researchers [10. was then mixed with HDPE and recompounded at 473 K and 300 rpm to prepare HDPE/manPE/CaCO3. Model CM-MTE 32) at 473 K and 300 rpm to make a masterbatch.high density polyethylene (manPE) as a compatibilizer via direct melt compounding in a twin-screw extruder. the samples were heated to 433 K and held in the molten state for 5 minutes to eliminate the influence of thermal history. 15. Based on these values. Maleic anhydride grafted high density polyethylene (Fusabond1 E MB265D) with a MFI of 12.9. and differential scanning calorimeter (DSC). The DSC was calibrated using indium with samples weights of 8–10 mg. The 25 wt% masterbatch DOI 10. Many researchers tried to analyze the nonisothermal kinetics [7–10]. All materials were used as received without purification.4. The results indicate that both manPE and well-dispersed CaCO3 particles would act as nuclei to induce heterogeneous nucleation and enhance crystallization rate. Nanoscale CaCO3 with particle size 15–40 nm and specific surface area greater than 40 m2/g were purchased from Nanomaterials Technology (Shanxi. HDPE/CaCO3. manPE and 20 wt% nanoscale CaCO3 were compounded with a twin-screw extruder (L/D ¼ 32. and graft level of 0. Wide-Angle X-Ray Diffraction Wide-angle X-ray diffraction (WAXD) were carried out using a Philips XRG-3000 generator with Ni-filtered ˚ Cu Ka radiation (k ¼ 1. with a twin-screw extruder at 473 K and 300 rpm.3. the characteristic X-ray peaks for neat HDPE were observed at the scattering angles of 21. All operations were carried out under nitrogen atmosphere.07 g/10 min (1908C 3 2. However.6. Taiwan. In addition to the sharp diffraction peaks. 30. 11] consider the effect of undercooling. Japan) polarized optical microscope (POM). Two blends of HDPE/manPE and HDPE/CaCO3 were also prepared with 25 wt% manPE and 5 wt% nanosized CaCO3. both parameters (U* and Kg) of Lauritzen-Hoffman were evaluated by Vyazovkin’ method. respectively. Taiwan) under trade name TAISOX1 9000 with a melt flow index (MFI) of 0. The sample melts were then subsequently cooled to 298 K at a cooling rate of 5. and 75 wt% HDPE. 24. 1 is the characteristic diffraction band of the amorphous POLYMER ENGINEERING AND SCIENCE— -2008 1269 Sample Preparation All materials were dried at 323 K in a vacuum oven for 6 h before compounding. The patterns were recorded at a scanning rate of 38/min. PerkinElmer Pyris 1 DSC. however.16 kgf. The samples were heated to 433 K and held in the molten state for 5 min. Continent Machinery Company.54 A). and (020) planes. In this article. and HDPE/manPE/ CaCO3 were investigated by wide-angle X-ray diffraction (WAXD). and 25 K/min.5–1 wt% was produced by Du Pont (USA). EXPERIMENTAL Materials Commercial grade high density polyethylene (HDPE) was supplied by Formosa Plastics Corporation (Taipei. which contained 5 wt% CaCO3.1002/pen . and cooled to room temperature at a cooling rate of 10 K/min. The samples on glass slides covered with slips were heated to 433 K to melt. ASTM D1238). the neat HDPE was also passed the extruder at the same conditions. 20. HDPE/manPE. Polarized Optical Microscopy Sample morphologies were observed under polarized light with a Nikon (Tokyo. (210). 10. Crystallization kinetics was described by different models taking undercooling into account. the aggregation of particles is formed in HDPE/CaCO3 blend in the absence of a compatibilizer.3 g/10 min (1908C 3 2. The manPE acts as a coupling agent to coat on the surface of nanoscale CaCO3 particles and dispersed in HDPE. Nonisothermal crystallization process is more complex than isothermal crystallization. ASTM D1238). The isothermal crystallization kinetics and equilibrium melting temperature were also studied. The effective activation energy was estimated by differential isoconversional method of Friedman. Before the data gathering. the shoulder on the Fig. D ¼ 40 mm. because the temperature is not constant. (200). which operated at an applied voltage of 30 kV and a current of 30 mA. respectively [12]. which correspond to the reflections from the (110).

3a–d. HDPE/manPE. HDPE/manPE. Spherulitic Morphology Polyethylene crystallites are known to be arranged in spherical aggregates [18] The spherulites formed with a cooling rate of 10 K/min for HDPE.68 2.1%). w is the mass fraction of HDPE in the blend. however.8.7 ˚ d-spacing. HDPE/CaCO3.4 36. (b) HDPE/manPE. This decrease in the peak intensity could be due to the decrease in crystallinity [13.06 3. The characteristic peaks of HDPE/manPE. which DOI 10. and HDPE/manPE/CaCO3. Figure 2 exhibits DSC heating scans of HDPE.94 2. and HDPE/manPE/CaCO3 are similar to those of neat HDPE as shown in Fig.46 4. and HDPE/manPE/CaCO3 were observed by a polarizing microscopy and shown in Fig. There are no new characteristic peaks or significant difference appearing in the X-ray patterns of the blends indicating that the crystalline structure of HDPE remains unchanged upon blending with manPE or CaCO3.6 21. HDPE/CaCO3.6 21.4 36. (b) HDPE/manPE. and the resulting spherulite size will be dependent upon the concentration of such nuclei.9 24.8 24.1. According to the previous studies. 2y 21.2 30. HDPE/CaCO3. regions.1002/pen HDPE/manPE HDPE/CaCO3 HDPE/manPE/CaCO3 1270 POLYMER ENGINEERING AND SCIENCE— -2008 .5 21.3 36.06 3. Each spherulite arises from a primary nucleus. (a) HDPE.FIG. 76.1 30. Sample HDPE Angle. reduces the crystallinity.08 3.9 24. 14] and will also be confirmed by the following DSC measurements. and HDPE/manPE/CaCO3 blends.8% vs.94 2.08 3.8 24. and (d) HDPE/manPE/CaCO3 blends. 17] The more dispersed CaCO3 particles in HDPE/manPE/CaCO3 provide the higher interfacial area and interaction between the polymer matrix and the CaCO3.3 30. WAXD patterns of HDPE. 85. 1 and Table 1. and HDPE/manPE/CaCO3.66 2. by heating to 433 K at a rate of 10 K/min. A 4. The incorporation of CaCO3. and 71. FIG. HDPE/CaCO3.2% for HDPE. HDPE/CaCO3. the heat of fusion of 100% crystalline HDPE is 295. The crystallinity of the HDPE was calculated according to the following relation: crystallinity ¼ DHm o WDHm (1) Melting Behavior The melting behaviors of HDPE and its blends were determined by DSC. and (d) HDPE/manPE/CaCO3 blends. The crystallinity does not change much by the addition of manPE (84. however.46 4.66 2.3 36. (c) HDPE/ CaCO3.46 4.95 2. All samples were cooled from the melt state at a cooling rate of 10 K/min and then followed TABLE 1. the intensity of the crystalline peaks of HDPE decreases as CaCO3 was added. HDPE/CaCO3. 1. which retard molecular mobility and a lowest crystallinity is obtained. The calculated crystallinity was 84. (c) HDPE/ CaCO3.69 2. HDPE/manPE. 2. and the crystallinity of manPE itself may account for this. DSC heating scan of (a) HDPE. CaCO3 particles can act as heterogeneous nuclei and form more nuclei than neat HDPE.3 30. The particles would reduce the mobility of polymer chain and result a lower crystallinity [16. As can be seen in Fig. HDPE/manPE. and HDPE/manPE/CaCO3. respectively.8. HDPE/manPE.95 2. Peak positions (as equivalent Bragg spacings d) for HDPE. 85. 1.45 hkl (110) (200) (210) (020) (110) (200) (210) (020) (110) (200) (210) (020) (110) (200) (210) (020) where DHm is the measured heat of fusion for the sample o and DHm is the heat of fusion for a 100% crystalline HDPE.8 J/g [15].

1002/pen perature because the more dispersed CaCO3 particles in blend induce more nuclei. Optical micrographs of HDPE and HDPE blends. and (d) HDPE/manPE/CaCO3. (a) HDPE. while at higher cooling rate the nuclei become active at lower temperature [10. 22]. 3b shows the spherulite size of HDPE increases with the addition of manPE. DSC nonisothermal measurement curves for HDPE/manPE/ CaCO3. POLYMER ENGINEERING AND SCIENCE— -2008 1271 . (b) HDPE/manPE. because there was more time to overcome the nucleation energy barriers. because both can act as a nucleating agent and therefore HDPE in blends started to crystallize earlier. Crystallization started at higher temperatures when cooling rate was lower. result in a smaller spherulite size (as shown in Fig. Similar morphological behavior was observed in HDPE and poly(octadecyl acrylate) blend [19]. It was observed that both To and Tp decreased with increasing cooling rate. 3c and d). (c) HDPE/CaCO3. Nonisothermal Crystallization Figure 4 shows the representative DSC scans of HDPE/manPE/CaCO3 blend on cooling from 433 K at various cooling rates.   R T dHc To dT dT   XT ¼ R T1 dHc dT To dT (2) FIG. Fig. However.FIG. The cooling rate dependence of the onset (To) and peak (Tp) of the crystallization exotherms is shown in Table 2. was calculated as the ratio of the exothermic peak areas [21. The relative crystallinity as a function of temperature. XT. HDPE in HDPE/manPE/CaCO3 stars to crystallize at a higher temDOI 10. 3. Consequently. 4. there may be regions surrounding a given nucleus where the probability of forming a second nucleus is low. The presence of maleic anhydride groups or CaCO3 in HDPE leads to an increase in To at a given cooling rate. 20]. It may be due to the low molecular weight manPE with lower viscosity is rejected outside the crystallizing regions in the melt.

1 386.37 3.1 385.90 1. based on the following equation: . 6.79 3. 5 could be transformed into a time scale.7 392.74 HDPE/manPE HDPE/CaCO3 FIG.9 388.68 3.2 391. The temperature abscissa in Fig.6 387.4 389.58 2.0 394. 6. as shown in Fig.5 389.2 387.6 388.9 391.8 392. Characteristic data of nonisothermal melt crystallization exotherms for HDPE and HDPE blends.5 386.6 394.3 393.5 393.5 394.7 388.1 393.7 389.2 393.2 393.4 392.TABLE 2.01 2.6 387.6 394.1 390. Cooling rate (K/min) 5 10 15 20 25 5 10 15 20 25 5 10 15 20 25 5 10 15 20 25 Sample HDPE To (K) 394.5 386.0 384.7 388.4 386.3 387.37 2.38 2. Figure 5 presents a representative relative crystallinity (XT) as a function of temperature for HDPE/ manPE/CaCO3.5 388.9 391.22 1.4 387.6 1/t1/2 (minÀ1) 1.4 388.28 1.9 392.2 392.2 385.8 393.3 390.6 394.69 2.4 393.0 390.31 1.0 388.8 392. Experimental relative crystallinity as a function of time at different cooling rate and Avrami analysis for HDPE/manPE/CaCO3.02 2.0 391. HDPE/manPE/ CaCO3 where T is an arbitrary temperature.87 3.4 394.3 395.3 Tp (K) 390.9 384.6 385.9 393.53 2.80 3.3 389.24 1.37 3.3 389.5 T1/2 (K) 390. dHc is the enthalpy of crystallization released during an infinitesimal temperature interval dT.1 385.40 2.8 388.9 388.



To À T .



(3) t¼.

F .

and na is the Avrami exponent. 4. 6. It can be seen clearly from Fig. Values of Ka and na were found by fitting experimental data of Xt to Eq.. In nonisothermal crystallization. (5) 1272 POLYMER ENGINEERING AND SCIENCE— -2008 DOI 10. 5. the shorter the time for completing the crystallization. defined as the time from the onset of crystallization to the time at which Xt is 50%. 6 that the higher the cooling rate.1002/pen . Jeziorny [26] assumed constant or approximately constant cooling rate and proposed the final form of the parameter characterizing the kinetics of nonisothermal crystallization: ln KJ ¼ ln Ka F FIG. The Avrami equation is expressed as Xt ¼ 1 À expðÀðKa tÞna Þ (4) where Xt is the relative crystallinity. and the results were shown in Table 3. where F is cooling rate. Ka and na do not have the same physical significance as in the isothermal crystallization. Table 2 also shows the half-time of crystallization (t1/2). The t1/2 value decreases with increasing cooling rate indicates the polymer crystallized faster when the cooling rate is increased. The relative crystallinity (Xt) of HDPE and its blends as a function of time are illustrated in Fig. Ka is the Avrami crystallization rate constant. because temperature changes constantly. The results will be discussed in more detail later.e. 1/t1/2) signifies the bulk crystallization rate and a lower 1/t1/2 value indicates slower crystallization. the 1/t1/2 for HDPE and its blends followed the order: HDPE/CaCO3 > HDPE/manPE/CaCO3 > HDPE/manPE > HDPE. This temperature changes affect the rate of both nuclei formation and spherulite growth. Experimental relative crystallinity as a function of temperature at different cooling rate for HDPE/manPE/CaCO3. The inverse value of t1/2 (i. At a given cooling rate. t is crystallization time. Xt can be calculated as the ratio between the area of the exothermic peak at time t and the total measured area of crystallization. Avrami Analysis Avrami equation [23–25] can be used to describe the nonisothermal crystallization.

42 0.9795 0.60 1.86 0.9923 0. respectively.93 9.649 1.27 0.9912 0. 7 and regression coefficient (R2) listed in Table 4.07 1.073 2.00 1.81 341.34 3. As can be seen in Fig.935 1.9870 0.9971 0. Cooling rate (K/min) 5 10 15 20 25 5 10 15 20 25 5 10 15 20 25 5 10 15 20 25 Sample HDPE na 1.99 2.99 2. When the cooling rates vary in a wide range.40 117. Avrami kinetics parameters.10 0.65 1.50 693.9843 0.85 6.991 1. However.9489 0.20 981.9687 Ozawa Model Considering the effect of cooling rate on the nonisothermal crystallization.62 2.31 1534. relation between ln[Àln(1 À XT)] and ln F is not good.9857 0.9598 0.00 8.25 0.34 0.9770 0.92 1.31 0.27 345.9742 0.9417 0.33 R2 0.76 65.022 1.29 0.74 15.9606 0. Ozawa modified the Avrami model from isothermal crystallization to the nonisothermal crystallization by assuming that crystallization occurs at a constant cooling rate and the model as following [27]:   no  Ko XT ¼ 1 À exp À F lnfÀ ln½1 À XT Šg ¼ ln Ko À no ln F (6a) HDPE/manPE HDPE/CaCO3 (6b) where Ko and no are Ozawa crystallization rate constant and Ozawa exponent.041 1. Ozawa treatment is essentially quasi-isothermal in nature.74 20.503 1.35 0.010 1.12 1350.36 0.9823 0.042 1.050 1. TABLE 4.374 2.22 449. It indicates that Avrami model is not suitable for the nonisothermal crystallization of HDPE and its blends.9451 0.13 164.9521 0. Ozawa kinetic parameters.88 25.9911 0.928 1.9871 0.54 5.26 0.95 2.840 2.37 Ko 307.69 1.9851 0.9855 0.67 1.321 1. 7.297 2.34 0.9534 0.9358 0.049 1.9839 0.41 0.043 1.9901 0.245 1.042 1. 4 seems to provide a good fit to experimental data based on regression coefficient (R2).9533 0.78 615.998 2.67 Ka (minÀ1) 0.02 46.32 65. The Ozawa kinetic parameters as well as regression coefficient (R2) are listed in Table 4.534 2.94 2.11 2.9608 0.05 2.28 0.11 2.259 2.54 1.06 2.9835 0. Sample HDPE Temperature (K) 372 375 378 381 384 387 390 369 372 375 378 381 384 387 390 372 375 378 381 384 387 390 372 375 378 381 384 387 390 no 0.36 0.87 1.9864 0.9761 0.28 0.044 1.040 1.956 1.9776 0.19 540.9809 0. KJ increased with increasing cooling rate for all samples. The Ko and no could be estimated from the y-intercept [(Ko ¼ exp(y-intercept/no))] and slope.60 1.83 0.9804 0.29 5.37 256.42 0. the selected XT values may have included secondary crystallization.TABLE 3.044 1.881 2.67 1.9185 0.33 0.71 1.35 0.538 2.042 1.32 0.43 0. Eq.985 1. Fig.55 208. Ozawa analysis based on the nonisothermal crystallization of HDPE/manPE/CaCO3.8963 0.53 326. the linear DOI 10.9884 0.9836 0.951 0.9886 0. HDPE/manPE/ CaCO3 The values of KJ are listed in Table 3.36 6.047 1.44 935.94 1.9792 0.9781 0.157 0.028 1.048 1. 6 shows an obvious deviation between the predicted curves based on the Avrami model and the experimental throughout the entire range.1002/pen HDPE/manPE/CaCO3 POLYMER ENGINEERING AND SCIENCE— -2008 1273 . The XT chosen at a given temperature includes the values on the earliest stage as well as the values from the end stage of crystallization due to variation in the cooling rates.043 R2 0. and Ozawa model seems inappropriate to describe the nonisothermal crystallization HDPE and its blends.9353 0.044 0. Figure 7 illustrates a typical plot of ln[Àln(1 À XT)] as a function of ln F for a fixed temperature.985 1.031 0.9731 0.82 14.9983 0.04 1.9643 0.01 2.9976 0.856 KJ 0.9914 0.9930 HDPE/manPE HDPE/CaCO3 FIG.9920 0.9806 0.

2 0. refers to the value of the cooling rate chosen at the unit crystallization time when the measured system amounts to a certain degree of crystallinity.61 1.8 F(T) 2.333 1.496 3. Plots of ln F verus ln t for different relative degree of crystallinity for HDPE/manPE/CaCO3.1002/pen .56 1.4 0. the equilibrium temperature was estioLHW mated by linear Hoffman-Weeks equation (Tm ). 1274 POLYMER ENGINEERING AND SCIENCE— -2008 HDPE/manPE HDPE/CaCO3 HDPE/manPE/CaCO3 DOI 10.9991 0.9981 0.9979 0.59 1.9998 0.6 0. the result is only the order of values of ‘‘crystallization rate.2 0.9935 0.9981 0. 30].996 1.660 a 1.58 1. Therefore.960 7.58 1.8 0.57 1.59 for neat HDPE. and HDPE/manPE/ CaCO3.59 1. 1.9979 0.7 0.5 0.9917 0. plotting ln F versus ln t (a typical plot is shown in Fig.783 1.3 0.9981 0.8 0.56 1. However.9991 0.186 2.62 1.9989 0.9960 0. 1.6 0. the values of F(T) follow the order: HDPE/CaCO3 < HDPE/manPE/ CaCO3 < HDPE/manPE< HDPE.3 0.9930 where the kinetic parameter.345 5.3 0.606 1. [31] combined Avrami and Ozwa methods [Eqs.54 R2 0.60 1. Ozawa model could successfully simulate the nonisothermal crystallization of polyethylene with narrower molecular distribution [28] but failed to those with broader molecular distribution [29.9961 0. The crystallization rate of a polymer depends mainly on its undercooling [10].9877 0.54 to 1.7 0.71 for HDPE/ CaCO3. neither 1/t1/2 nor F(T) considers the effect of undercooling. [11] compared nonisothermal experimental data in terms of the degree of undercooling DTc. The growth rate and instantaneous nucleation rate are assumed to be constant by Avrami equation.4 0. and 1.338 2.57 to 1.702 6.9953 0.71 1. and 410. The undercooling follows the order: HDPE > HDPE/manPE > HDPE/ CaCO3 > HDPE/manPE/CaCO3. and the values were 416. F(T).5 0. and the values of F(T) and a (Table 5) could be obtained from the slopes and intercepts of these lines. respectively.9964 0. but be a function of temperature by Ozawa equation.62 for HDPE/manPE.6 0.59 1.203 3.5.939 2.9939 0.7 0.3 0.60 1.9920 0.4 0. 8.3.117 4.65 1.9944 0.51 1.411 4. and it indicates that the ‘‘crystallizability’’ follows the order: HDPE/manPE/ CaCO3 > HDPE/CaCO3 > HDPE/manPE > HDPE.61 1. respectively. HDPE/manPE.5 0. 411. Sample HDPE Xt 0. though it is difficulty to modeling the development of crystallization during polymer processing. The value of a varies from 1. Figure 9 shows the undercooling needed to be imposed to reach 50% relative crystallizaoNLHW tion (XT ¼ 0.61 for HDPE/manPE/CaCO3. The trend is similar to the results obtained from 1/t1/2.67 1.63 1.7 0. Nadkarni et al.9919 0.55 1.019 3.568 7.658 4. To combine the two equations with different assumptions seems not justified.51 to 1.938 2.’’ In previous study [9]. Liu model seems appropriate to analysis the nonisothermal crystallization kinetic. TABLE 5.9995 0. that is Tm À T1=2 .525 1. 8) yielded a good linear relationship between ln F and ln t.8 K for HDPE.5 0.FIG.6 0.2. a is the ratio of Avrami exponent (na) to the Ozawa exponent (no). Value of F(T) and a for HDPE and blends.518 7. At a given degree of crystallinity.9944 0.8 0.762 4.9993 0.60 to 1.080 5.436 3. indicating that at unit crystallization time.54 1. Liu Model Liu et al. 4 and 6a] to deal with the nonisothermal crystallization behavior and its form is given as follows:  no n1 o K na ln F ¼ ln o a À ln t (7a) n Ka no  no n1 o K FðTÞ ¼ o a (7b) n Ka a¼ na no (7c) At the same relative degree of crystallinity. it suggests that the crystallization rate follows the order: HDPE/CaCO3 > HDPE/manPE/CaCO3 > HDPE/manPE > HDPE.740 5.606 3. a higher cooling rate is required to reach a higher degree of crystallinity. The value of F(T) increases with increasing degree of crystallinity.56 1.2 0.64 1.60 1.9987 0.852 2.66 1. HDPE/CaCO3. 411.58 1.5).9996 0.740 3.61 1.9957 0.4 0.57 1.2 0.9912 0. enhance crystallization [32]. and the slope P o indicates a process sensitivity factor. and DEXt is the effective energy barrier of the process for a given value of Xt. and HDPE/ manPE/CaCO3 are 21. However. and the onset crystallization temperature [10]. the values of dXt/dt at a specific Xt are correlated to the corresponding crystallization temperature at this Xt. which means the crystallization becomes more difficult with increasing Xt. and the data may be fitted to a linear equation: o o DT c ¼ Tm À To ¼ PF þ DTc (8) o where the intercept DTc signifies the inherent crystallizability of the polymer. where available. 15. The nanosized CaCO3 particles are well dispersed in HDPE/ manPE/CaCO3.1. the undercooling should be calculated as the difference between the equilibrium melting temperature. a straight line can be obtained by plotting dXt/dt versus 1=TXt and the slope is ÀDEXt =R. DTc ¼ Tm À To as a function of cooling rate. The o FIG. The maleic anhydride groups of manPE might associate through some interactions such as hydrogen bonding to form effective nuclei where dXt/dt is the instantaneous crystallization rate as a function of time for a given value of the relative crystallinity (Xt). TXt . 16. Inorganic CaCO3 is an effective nucleation agent and will induce heterogeneous nucleation to enhance crystallization of polymer [33].7. R is the universal gas constant.0 K. and 15. The activation energy is negative. HDPE/manPE. 10. The differential isoconversional method of Friedman [38] and the advanced integral isoconversional method of Vyazovkin [39. 11. which indicates the crystallization increases with decreasing temperature. Effective Activation Energy Some methods have been suggested to estimate the effective energy barrier in nonisothermal crystallization [34–36]. However. that is. HDPE/CaCO3. It can be seen that the experimental activation energy increases with the extent of Xt. The values of DTc for HDPE. Undercooling to reach 50% relative crystallinity for HDPE and HDPE blends at various cooling rate. 40] are appreciated to estimate the effective activation energy. 10. which also suggest ‘‘crystallizability’’ of the blends followed the order: HDPE/manPE/CaCO3 > HDPE/ CaCO3 > HDPE/manPE > HDPE.2. 9. DOI 10. The Friedman equation can be expressed as follows: ln   dXt DEXt ¼ constant À dt Xt RTXt (9) FIG. to drop the negative sign in cooling process may result in errors [37].1002/pen POLYMER ENGINEERING AND SCIENCE— -2008 1275 . defined as the temperature difference between the melting peak temperature in the heating scan and the temperature at onset of crystallization in the cooling scan. 11. and the blend has highest crystallization ability. Dependence of the effective activation energy and temperature on the crystallization conversion extent for two binary blends. The dependence of the effective activation energy on conversion based on Friedman equation was shown in Fig. being the degree of supercooling required in the limit of zero cooling rate. FIG. At various cooling rates. The Friedman equation [38] was applied to estimate the dependence of the effective activation energy on conversion in this study. The variation of this parameter DTc with the cooling rate is shown in Fig.

The transition temperature is due to a change in crystallization mechanism from regime I (higher temperature) to II (lower temperature).9856 0. which is close theoretical ratio 2. At a specific Xt.9788 0.56 0. U* is the diffusion activation energy for the transport of crystallizable segments at the liquid–solid interface.30 R 2. This implies that the incorporation of nucleating agents could lead to the alteration in crystallization behaviors.73 1.9 7.55 0.98 1.9815 0. However. the trend among three HDPE blends is more complex.9 6.95 2.98 3 105 and 1.3 re 3 10À2 (J/m2) 3. o Tm is the equilibrium melting temperature. 11. This trend suggests that maleic anhydride groups and CaCO3 particles may act as heterogeneous nuclei for the crystallization of HDPE and accelerate the crystallization process. the activation energy of three HDPE blends with the addition of manPE or CaCO3 is smaller than that of the neat HDPE.9823 0. 40] used the results of the effective activation energy on temperature to estimate the parameters (Kg and U*) of the Lauritzen-Hoffman theory [41] and derived the following equation: ðln GÞ DEXt ¼ ÀR dð1=TÞ ¼ U Ã folding surface free energy (se). 10 with the results of dependence of the effective activation energy on temperature. which is in accordance with the results (383 K) reported by Tjong and Bao [1]. which were obtained from isothermal calorimetric measurements [1].82 0. R is the gas constant. which is similar to the results observed in PE/montmorillonite [42] and poly(butylene terephthalate)/Attapulgite nanocomposites [43].9901 0. The result also confirms that transition is the change in the crystallization mechanism from regime I to regime II [12].17 1. the addition of manPE or CaCO3 particles gives rise to the TABLE 6. 4. Crystallization parameters of HDPE.13 3 105 and 1. There is a transition region between 382 and 386 K for neat HDPE.05 1. It can also be found from Fig.39 0. The DEXt involves two factors: nucleation and diffusion of crystallizable chains to the crystal front. Regime HDPE HDPE/manPE HDPE/CaCO3 HDPE/manPE/CaCO3 I II I II I II I II Kg 3 105 (K2) 3.58 3.FIG. which can be related to the product of lateral (s) and where b is the width of the chain. 12 that the transition temperature increases with the addition of manPE or CaCO3.11 Â 10À10 m for HDPE [44].1002/pen .83 3 105) of neat HDPE in Table 6 are close to those values (3. Tg ¼ 163 K [35].13 0. Dependence of the effective activation energy on average temperature and fitted by Vyazovkin’s method.76 1. 12. s ¼ 1. As seen in Table 6. dependence of the effective activation energy on temperature can be evaluated by replacing Xt with an average temperature.5 5.58 3 105).28 R2 0.1 12. [45] k is the Boltzman constant.41 0. according to Vyazovkin’s method [39.88 1. The obtained Kg values can be used to determine the fold surface free energy (re): [41] Kg ¼ Kg ¼ o 4bsse Tm kDhf o 2bsse Tm kDhf ðregime IÞ ðregime IIÞ (11a) (11b) T2 ðT À T1 Þ2 þ Kg R o o ðTm Þ2 À T 2 À Tm T o ðTm À TÞ2 T (10) G is the growth rate.08 0. The Kg values (3. and the results are also shown in Fig. Vyazovkin [39. The fold surface free energy (se) was estimated by Eq. Kg is the nucleation parameter. The values Kg and U* in regime I or II can be estimated by fitting Eq. 9 and tabled in Table 6. Figure 12 shows the activation energy dependence on temperature. and the results are shown in Table 6. T! ¼ Tg À30 K is the hypothetical temperature below which viscous flow ceases and Tg is glass transition temperature. The ratio (R) of Kg at regime I to regime II is 1.87 U* (KJ/mole) 5. and Dhf is the enthalpy of fusion [46].9857 0.86 0.9874 0.54 0.07 Â 10À2 J/m2 for HDPE. 40].83 1.58 0.4 9.87–2.17.9923 1276 POLYMER ENGINEERING AND SCIENCE— -2008 DOI 10.

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