Formation Mechanism of Crystal Morphologies in LLDPE/HDPE Blends Investigated via Water-Assisted and Conventional Injection Molding

Bin Wang, Han-Xiong Huang Laboratory of Micro Molding and Polymer Rheology, Center for Polymer Processing Equipment and Intellectualization, South China University of Technology, Guangzhou 510640, Peoples Republic of China

The LLDPE/HDPE blends with two different weight ratios as well as pure LLDPE were molded by means of water-assisted and conventional injection molding (WAIM and CIM) in terms of their different thermal elds. The formation of the crystal morphology in the molded parts was investigated by a scanning electron microscope. The results showed that banded spherulites formed in the WAIM and CIM pure LLDPE parts. Banded spherulites of LLDPE coexisted with the randomly oriented lamellae of HDPE for LLDPE/HDPE blend parts with lower HDPE content at higher cooling rates, whereas a banding to nonbanding morphological transition occurred for LLDPE component (particularly for blend with higher HDPE content) at lower cooling rates. The heterogeneous nucleation effect of HDPE component on LLDPE component was responsible for the banding to nonbanding morphological transition by hindering the twist of LLDPE lamellae. It was interesting to nd that the thermal effect, rather than the shear effect, was the main factor for the formation of crystal morphologies in both CIM and WAIM blend parts.
POLYM. ENG. SCI., 52:117124, 2012. 2011 Society of Plastics Engineers

INTRODUCTION Banded spherulites have been observed in both achiral polymers (such as polyethylene and a-poly(vinylidene uoride)) and chiral polymers [such as poly(l-lactide)] [14]. Moreover, an interesting nonbanding to banding morphological transition has been reported for several semicrystalline polymers upon blending with a miscible amorphous polymer component due to the specic interactions between the two polymer components [47]. The forma-

Correspondence to: Han-Xiong Huang; e-mail: mmhuang@scut.edu.cn Contract grant sponsor: National Natural Science Foundation of China; contract grant number: 20874031; contract grant sponsor: Guangdong Provincial Natural Science Foundation; contract grant number: 06025643. DOI 10.1002/pen.22053 Published online in Wiley Online Library (wileyonlinelibrary.com). C V 2011 Society of Plastics Engineers

tion mechanism of banded spherulites for polymers has been widely investigated and is still an interesting topic of research and controversy. It is generally accepted that the banded spherulites are attributed to periodic twisting of lamellae along the radial growth direction of the spherulites or screw dislocation or rhythmic crystal growth, among which lamellae twisting is widely used for the interpretation of radial banding [811]. Most previous researches on banded spherulites were, however, carried out in the quiescent state. In fact, they could also form during polymer processing, as conrmed in the literatures [1214]. To the best knowledge of the authors, there was no report of banded spherulites formation for polymer blends during processing. Recently, there has been increasing interest in studying the crystallization behavior and crystal morphology of miscible semicrystalline/semicrystalline polymer blends [15, 16]. It is reported that the difference in the melting points (Tms) of the two components has a signicant inuence on the crystallization kinetics and morphology when the blends crystallize from the homogenous melt, and the two components can crystallize simultaneously depending on blend composition and crystallization temperature when the Tm difference is small. It is thus expected that the crystal morphology of the individual component can be manipulated by mixing components with different Tms and by changing the crystallization temperature or the composition of the blends. Considering the fact that a nonbanding to banding morphological transition can take place for several semicrystalline polymers upon blending with a miscible amorphous polymer component, the authors are inspired to explore the blending effects on the crystal morphology of miscible semicrystalline/semicrystalline polymer blends, i.e., linear low density polyethylene/high density polyethylene (LLDPE/HDPE) blends in this work. Then, the polymer blends were molded by means of water-assisted and conventional injection molding (WAIM and CIM) in terms of their different thermal elds to investigate the inuence of cooling rate on the formation of the crystal morphology in the polymer blend parts.

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FIG. 1. Schematics of WAIM part and positions for SEM observation. [Color gure can be viewed in the online issue, which is available at wileyonlinelibrary.com.]

EXPERIMENTAL Materials and Sample Preparation A LLDPE (grade 7042, Maoming Petrochemical Co.) with weight-average molecular weight (Mw) of 2.1 3 105 g/mol and a melt ow index (MFI) of 2.0 g/10 min (1908C, 2.16 kg), and an HDPE (grade TR480, Maoming Petrochemical Co.) with Mw of 4.5 3 105 g/mol and an MFI of 0.11 g/10 min (1908C, 2.16 kg) were used in this study. Melt blending of LLDPE/HDPE at two ratios (90/10 and 70/30, w/w) was conducted using a corotating twinscrew extruder with a diameter of 20 mm. The temperatures were maintained at 130, 150, 170, 170, 170, 170, and 1658C from the hopper to the die. After being pelletized and dried, the blends were molded by WAIM using a newly developed WAIM system in our laboratory, which mainly consists of a water injection unit and an 80-ton conventional injection molding machine with a highest injection rate of 84 cm3/s [17]. The processing parameters were set as follows: the melt temperature was 1808C, the short-shot size 68.5 vol%, the water injection delay time 5 s, the water injection pressure 18.5 MPa, and the water packing time 8 s. Both the mold and the
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water were kept at room temperature in all experiments. The conventional injection molding (CIM) was also conducted using the same processing parameters except that the melt shot size was 100 vol%, and the polymer melt was not exposed to water penetration and water-assisted packing process. Moreover, pure LLDPE was molded by the same WAIM and CIM processes for the purpose of comparison. Characterization The miscibility between LLDPE and HDPE was determined using a differential scanning calorimeter (DSC, Netzsch 204) under a nitrogen environment. The samples with about 5 mg, which were cut from the pelletized granules, were heated from 20 to 1808C at a heating rate of 308C/min and held there for 3 min to erase any thermal history, then cooled to 208C at a cooling rate of 108C/min and again heated to 1808C at a heating rate of 108C/min. The crystal morphologies of both WAIM and CIM parts were studied by preferential etching of the amorphous phase. Before etching, the WAIM and CIM parts were cut into segments of 5 mm length at a position near the gate (as shown in Fig. 1). The segments were freezeDOI 10.1002/pen

fractured along the ow direction in liquid nitrogen. Subsequently, the specimens were etched following the permanganic etching technique developed by Olley and Bassett [18]. After the specimens were coated with gold, their fractured surfaces were examined using a scanning electron microscope (SEM, FEI Nova NanoSEM 430) at an accelerating voltage of 5 kV. RESULTS AND DISCUSSION Heterogeneous Nucleation In binary semicrystalline/semicrystalline polymer blends, upon cooling, the component with higher Tm usually crystallizes rst from the melt, followed by the crystallization of the lower-Tm component. However, for LLDPE/HDPE blends investigated in this work, the crystallization of both HDPE and LLDPE components interacted and thus usually only one exothermic peak was observed, as shown in Fig. 2a. Moreover, it is clearly observed from Fig. 2a that the onset of crystallization of the LLDPE component in LLDPE/HDPE blends was shifted to higher temperatures compared with that of pure LLDPE. This may be due to the heterogeneous nucleation effect of the HDPE component on the LLDPE component or the cocrystallization. However, relatively large difference of the Mws exists between the two PEs used in this work. Moreover, as will be described latter, banded spherulites of the LLDPE component formed in both outer and inner zones, where cocrystallization may occur, of the WAIM 90/10 LLDPE/HDPE blend parts. So the cocrystallization can be ruled out in this work. Subsequent melting behavior of LLDPE/HDPE blends was studied after the nonisothermal crystallization, and the results are shown in Fig. 2b. As can be seen in Fig. 2b, only one melting peak was observed for both 90/10 and 70/30 blends, which may be ascribed to the overlap of the melting peaks of the two polymers due to closeness in their Tms. Crystal Morphology in CIM Pure LLDPE and LLDPE/ HDPE Blend Parts Figure 3 shows the representative SEM micrographs of different zones of the CIM pure LLDPE part. It was interesting to nd that banded spherulites, which were usually reported in quiescent melt-crystallization process, formed in the outer zone (Fig. 3a), intermediate zone (Fig. 3b), and core zone (Fig. 3c) of the pure LLDPE part. Both band spacing and diameter of the banded spherulites were observed to increase with the distance from the skin of the LLDPE part, whereas the distribution density of banded spherulites showed an inverse tendency. The crystal morphologies in the CIM LLDPE/HDPE blend parts were found to be different from that in the pure LLDPE part. As shown in Fig. 4, randomly oriented lamellae
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FIG. 2. (a) DSC crystallization traces and (b) melting traces for LLDPE/HDPE blends with various HDPE contents (curves are labeled with the percentage by weight of HDPE).

structures were dominant in both outer and core zones for both 90/10 and 70/30 blend parts. For the 90/10 blend part, many long straight lamellae clusters were observed in both outer zone (Fig. 4(1)a) and core zone (Fig. 4(1)b). Moreover, one observed dendriform lamellae clusters in the outer zone, featuring the growth of many lamellae on the lateral surface of a lamellae at the center. Note that many curved lamellae were observed in the core zone, despite that the long straight lamellae clusters were dominant. However, only long straight lamellae clusters were observed in both outer zone (Fig. 4(2)a) and core zone (Fig. 4(2)b) for the 70/30 blend part. The observed long straight lamellae clusters were attributed to the growth of the LLDPE component on the lateral surface of the HDPE lamellae as a result of heterogeneous nucleation. Crystal Morphology in WAIM Pure LLDPE and LLDPE/ HDPE Blend Parts The crystal morphologies in different zones of both WAIM pure LLDPE and LLDPE/HDPE blend parts are shown in Fig. 5. As can be directly observed in Fig. 5(1)a, (1)b, and (1)c, banded spherulites formed in all three zones (outer zone, core zone, and inner zone) of the WAIM pure LLDPE part. The diameter of the banded spherulites in the outer zone (Fig. 5 (1)a) was found to be similar to that in the inner zone (Fig. 5(1)c), whereas larger diameter banded spherulites were observed in the core zone (Fig. 5(1)b). As can be seen from Figs. 3 and 5(1), banded spherulites formed in both CIM and WAIM
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the core zone (Fig. 5(2)b) of the 90/10 blend part, one observed that banded spherulites with irregular bands were surrounded by randomly oriented lamellae structures, whereas only randomly oriented lamellae structures were observed in the core zone for the 70/30 blend part, as shown in Fig. 5(3)b. Randomly oriented lamellae structures were dominant both in the outer zone (Fig. 5(3)a) and inner zone (Fig. 5(3)c) for the 70/30 blend part, and banded spherulites were nearly indiscernible in these two zones. Formation Mechanism of LLDPE Banded Spherulites It is necessary to observe the band spherulites at the level of lamellae structures for the purpose of exploring their formation mechanism. Thus, a fully grown banded spherulite in the CIM pure LLDPE part was observed by SEM with higher magnication and the result is shown in Fig. 6. As can be seen, the peak regions and valley regions appeared alternatively. The peak regions were observed to be composed of C-shaped curved lamellae, indicating the lamellae twisting in the radial direction of banded spherulites [11]. In other words, the periodical bands in LLDPE spherulites were resulted from lamellae twisting which was similar to the SEM results in gas-assisted injection molded HDPE [13]. Moreover, lamellae twisting was also responsible for the formation of banded spherulites in the WAIM LLDPE/HDPE blend, as conrmed in Fig. 5(2)b. Banding to Nonbanding Morphological Transition in LLDPE/HDPE Blend as a Result of Heterogeneous Nucleation As mentioned in the Introduction section, banded spherulites formed in some miscible semicrystalline/amorphous polymer blends due to the specic interactions between the two polymer components, whereas nonbanded spherulites formed in the pure crystalline polymer component. However, in this work, a contrary result was observed for semicrystalline/semicrystalline polymer blends. That is, banded spherulites formed in the pure LLDPE, whereas a banding to nonbanding transition occurred for the LLDPE upon blending with the HDPE. This can be interpreted as follows. Compared with the banded spherulites of the LLDPE formed via homogenous nucleation, the banding to nonbanding morphological transition for the LLDPE upon blending with the HDPE can be ascribed to the heterogeneous nucleation effects of the HDPE component on the LLDPE component. Figure 7 schematically shows the crystallization processes via homogeneous and heterogeneous nucleation. In the crystallization process via heterogeneous nucleation, many lamellae of the LLDPE grew simultaneously on the lateral surface of the lamellae of the HDPE, and propagated outward radially [19]. Consequently, the formation of nonbanded spherulites in the LLDPE/HDPE blend can be interpreted from the following three aspects. First, the lamellae of the LLDPE component in the spherulites
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FIG. 3. SEM micrographs in (a) outer zone, (b) intermediate zone, and (c) core zone of CIM LLDPE part.

pure LLDPE parts. However, it was not the case for LLDPE/HDPE blend parts. In both outer zone (Fig. 5(2)a) and inner zone (Fig. 5(2)c), banded spherulites were observed for the 90/10 blend part, but the bands were irregular compared to those of the WAIM pure LLDPE part. In
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FIG. 4. SEM micrographs in (a) outer zone and (b) core zone of CIM (1) 90/10 and (2) 70/30 LLDPE/ HDPE blend parts.

formed via heterogeneous nucleation would be expected to be more densely packed than that formed via the homogeneous nucleation, which was unfavorable for the branching and splaying process. Thus, the number of screw dislocations in heterogeneously nucleated spherulites would be expected to be much less than those in homogeneously nucleated spherulites. Secondly, the number of tie chains between two adjacent LLDPE lamellae increased in heterogeneously nucleated spherulites compared to those in homogeneously nucleated spherulites, due to more densely packed lamellae. As a result, lamellae twisting in heterogeneously nucleated spherulites would be expected to be hindered due to the fact that the lamellae were linked by more tie chains. Thirdly, the onset of crystallization of the LLDPE component was shifted to higher temperatures due to the heterogeneous nucleation effect of the HDPE component on the LLDPE component, as shown in Fig. 2a. As suggested by Keith and Padden [2], it was unfavorable for banded growth at a relatively low supercooling. From the foregoing, non-banded spherulites formed for the LLDPE component if it crystallized via heterogeneous nucleation.

Comparison of Crystal Morphology Development Between CIM and WAIM LLDPE/HDPE Blend Parts As shown in Figs. 4, 5(2), and 5(3), nonbanded spherulites were dominant in both CIM 90/10 and 70/30
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LLDPE/HDPE blend parts and nonbanded spherulites gradually dominated in the WAIM LLDPE/HDPE blend parts with increasing the HDPE content from 10 to 30 wt%. The crystal morphology development in both CIM and WAIM LLDPE/HDPE blend parts can be interpreted in terms of the thermal elds arising during the CIM and WAIM processes. Figure 8 schematically displays the thermal elds in both CIM and WAIM. It is well known that the CIM is essentially a owinduced non-isothermal crystallization process for semicrystalline polymers. In this work, the cavity of the mold used had a relatively large diameter (18 mm), which led to relatively low shear rates and large bulk heat of the melt. So after the melt lling, the cooling rates of the melt, especially that in the core zone, were low, and the LLDPE component crystallized via heterogeneous nucleation on the HDPE lamellae, which resulted in the formation of non-banded spherulites. Even though the shearinduced structures might form, they would relax fast due to low cooling rates. Note that as shown in Fig. 4(1)b, few spherulites with irregular bands were observed in the core zone for the 90/10 blend part. This may be explained as follows. The melt in the core zone stayed at higher temperatures for a relatively long time due to much lower cooling rate. Thus the nucleation density of the HDPE crystallites was relatively low, and some LLDPE melt could crystallize via homogenous nucleation, which resulted in the formation of irregular banded spherulites.
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FIG. 5. SEM micrographs in (a) outer zone, (b) core zone, and (c) inner zone of WAIM (1) LLDPE, (2) 90/10 LLDPE/HDPE blend, and (3) 70/30 LLDPE/HDPE blend parts.

However, when the HDPE content was increased to 30 wt%, the nucleation density of HDPE crystallites would be high enough to suppress the homogenous nucleation of the LLDPE melt and thus only nonbanded spherulites formed, as conrmed in Fig. 4(2)b. During the WAIM, the thermal eld was quite different from that in the CIM [20]. Because of the penetration of high-pressure water, a lot of heat in the melt was transferred to the water. Moreover, the residual wall thickness (about 3 mm) of the WAIM part was much smaller than the cross-section radius (9 mm) of the CIM part. As a result, the WAIM parts cooled much faster than the CIM parts did. Both in outer and inner zones, the LLDPE and HDPE components could crystallize almost simultaneously due to high cooling rates. As a result, banded spherulites formed in these two zones for the 90/10 blend part. However, banded spherulites were indiscernible in the aforementioned two zones for the 70/30 blend part. This
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FIG. 6. SEM micrograph of banded spherulites of CIM pure LLDPE part with higher magnication.

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may be due to the fact that the periodical twisting of the LLDPE lamellae was hindered by the increased HDPE crystallites. In the core zone, the cooling rate was not high enough, and the HDPE component could crystallize rst from the melt, followed by the crystallization of the LLDPE component. Consequently, nonbanded spherulites dominated the core zone of the 70/30 blend part due to the heterogeneous nucleation effect of the HDPE component on the LLDPE component. However, banded spherulites still formed in the core zone for the 90/10 blend part, possibly owing to the fact that the HDPE content was low and some LLDPE melt could crystallize by homogenous nucleation. But, it was obviously shown in Fig. 5(2)b that the periodical twisting of the LLDPE lamellae was hindered by the surrounding randomly oriented lamellae. It should be noted that, during the WAIM, the shear rate of the melt in the outer zone was similar to that in the corresponding zone during the CIM, since the observed position for SEM was lled during the partial melt lling stage (similar to the melt lling process in CIM). However, as can be seen from Figs. 5(2)a and 4(1)a, the resulting crystal morphology in the outer zone of the WAIM 90/10 blend part was quite different from that in the corresponding zone of the CIM counterpart, due to the difference of the thermal elds between the two molding methods [20]. It is thus concluded that the thermal effect, rather than the shear effect, was the main factor for the formation of crystal morphologies in both CIM and WAIM blend parts.

FIG. 8. Schematics of (1) temperature elds and (2) cooling rate elds in (a) CIM and (b) WAIM processes.

CONCLUSIONS The crystal morphology of both water-assisted and conventional injection molded (WAIM and CIM) parts were investigated in terms of the different thermal elds arose during the two molding methods. It was found that banded spherulites were formed in both WAIM and CIM pure LLDPE parts, and they could also form in the LLDPE/HDPE blend parts with lower HDPE content at higher cooling rates. A banding to non-banding morphological transition occurred for the LLDPE component (particularly for the blend with higher HDPE content) at lower cooling rates due to the heterogeneous nucleation effect of the HDPE component on the LLDPE component. Furthermore, the thermal effect, rather than the shear effect, was the main factor for the formation of crystal morphologies in both CIM and WAIM blend parts. REFERENCES
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FIG. 7. Schematics of crystallization processes via (a) homogeneous nucleation for pure LLDPE and (b) heterogeneous nucleation for LLDPE/HDPE blend.

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