# The Effect of Annealing on the Structure and Electric Performance of Polypropylene Films

Authors: Xiying Dai; Zhaoliang Xing; Wei Yang; Chong Zhang; Fei Li; Xin Chen; Chen Li; Jianjun Zhou; Lin Li
Journal: International Journal of Polymer Science
 (2022)

---

## Abstract

Biaxially oriented polypropylene (BOPP) and uniaxially oriented polypropylene (UOPP) films were annealed. The effect of annealing temperature (Ta) on dielectric strength was studied. The electric breakdown strength (Eb) of BOPP and UOPP films changes in a quite different trend with the annealing process. Eb of BOPP films decreases with the increase in Ta, whereas Eb of UOPP films increases first and then decreases with Ta. The structural changes during annealing were investigated. The crystallinity rises with Ta, while the orientation degree and Eb show a similar trend with Ta. Although the crystallinity and crystal structure can affect Eb of polypropylene films, the orientation of chain segments has a much larger correlation with Eb. Our results indicate that the deterioration of the metallized BOPP film capacitor may originate from the orientation degree decrease of chain segments after experiencing high temperature.


---

## Body

## 1. Introduction

Biaxially oriented polypropylene (BOPP) thin films are widely used in metallized film capacitors due to their extremely low dielectric loss (0.02%) and high dielectric strength (720 kV mm−1) [1–3]. Furthermore, metallized film capacitors have the properties of self-healing, which have promoted a wide application of metallized BOPP film capacitors in ultrahigh voltage flexible direct current (DC) power grid, high-speed railway, and new energy electric vehicles [4, 5]. Increasing the energy density and service temperature of metallized film capacitors is the endless pursuit of producers and customers [6, 7]. The energy density of the metallized film capacitor is determined by the dielectric constant and the electric breakdown strength (Eb) [8, 9]. The dielectric constant at a specific frequency and temperature is hard to be improved since the dipole or polarization is the intrinsic properties of polypropylene, while Eb can be affected by the processing parameters during BOPP manufacturing. Eb can be modified by changing the thickness, crystallinity, and tensile strength of BOPP films [10]. Eb can also be improved with a higher biaxially stretching ratio [11].When the metallized BOPP film capacitor experiences excessive voltage aboveEb, a point defect short circuit between metallized electrodes of the capacitor can occur. The metallic layer of electrodes evaporates rapidly due to arc discharge together with localized high temperature. The elevated temperature will considerably reduce the lifetime expectancy of metallized polymer film capacitors [12]. Thermal aging is one of the main failure mechanisms in polymeric film capacitors [13, 14]. Most studies concentrated on the aging of metallized film capacitors at a high temperature by monitoring the changes in their basic parameters [15, 16]. Capacitance and equivalent series resistance were monitored as the parameters that reflect the aging process [17, 18]. Basically, some of the parametric changes can be traced from the structure variation of the BOPP film [19]. However, although the performance of polypropylene (PP) capacitors during aging has been studied carefully, the structure evolution of the BOPP film during aging is not clearly investigated, which can be studied by annealing the BOPP film separately [20].Annealing is an important process to modify the performance of plastics. During annealing, the oriented chain relaxes accompanied with the re-arrangement of chain segments, resulting in a variation of the structure and performance. A uniaxially oriented polypropylene (UOPP) film is a base film for preparing microporous films by stretching. To prepare microporous film with uniform pore size, the UOPP film should be annealed first to modify the crystallinity and orientation degree before stretching. Some studies showed that both the orientation degree and crystallinity increased with annealing temperature (Ta) [21, 22]. After annealing, the content of defects in crystals was decreased, the orientation of the crystalline phase was increased, and microcrystals formed in the amorphous between primary lamellae [23]. While some proposed that the amorphous part could be divided into mobile amorphous fraction and rigid amorphous fraction. Annealing promoted the formation of looser mobile amorphous fraction and more rigid amorphous fraction by the microstructural re-arrangement [24]. Although there were some studies investigating the structure evolution of annealing on UOPP film, few studies concentrated on the annealing behavior of produced BOPP film. While the structure change after annealing is vital to understand the performance deterioration of metallized BOPP film capacitor. Also, no one has ever studied the dielectric and electric breakdown properties of UOPP film. Although both BOPP and UOPP are oriented films, various manufacturing art has endowed the two kinds of films with different crystal structures. The influence of crystal structures on the dielectric properties of polypropylene has been investigated a lot. However, the differences of oriented crystal structures between BOPP and UOPP, as well as the primary factor of the oriented crystal structures on impacting the breakdown strength have not been well studied.In this article, two kinds of oriented PP films were annealed at various temperatures, and studies were carried out to reveal the relationship between structure and dielectric strength. It is expected that our results can provide guidance for understanding the performance variation of metallized film capacitor.


## 2. Experimental Section

BOPP films with a thickness of 8μm were obtained from Tongfeng Electronics (Tongling, China). The BOPP films were commercial products for metalized PP film capacitors. UOPP films with a thickness of 16 μm were obtained from Cangzhou Mingzhu Plastic Co. Ltd. (Cangzhou, China). The UOPP films were prepared by melt casting at a large die draw ratio with the properties of hard elastic, which could be used as base films for preparing uniaxially stretched PP microporous films. BOPP and UOPP films were rolled to anneal at 100–150°C for 1 hour before further characterized, which simulated the state when PP films were rolled in the capacitors.The dielectric properties were measured using an impedance analyzer (Concept 40, Novocontrol GmbH, Montabaur, Germany) at room temperature from 107 to 102 Hz. Eb was conducted on the Dielectric Withstand Voltage Test System (Beiguang Jingyi Instrument Equipment Co., Ltd, Beijing, China). The leakage current was measured by a combination of power supply (Keithley, 2290-10) and System SourceMeter™ (Keithley, 2635B). The films were tested in insulating oil at room temperature. The two-parameter Weibull distribution was employed to analyze the DC breakdown strength of samples from the experimental data.Differential scanning calorimetry (DSC) measurements were taken with a DSC (PerkinElmer, DSC 8000) at 10°C minute−1. Indium and tin were employed for the temperature calibration. Samples of ~3.0 mg were sealed in aluminum pans and a nitrogen gas purge with a flux of ~20 mL minute−1 was used to prevent oxidative degradation of samples during the heating run. The crystallinity was calculated using the following equation:
(1)Xc=∆Hf∆Hfo.where ∆Hf is the melting enthalpy of α form crystals, ∆Hfo (165Jg−1) is the standard melt enthalpy of α form crystals.Wide-angel X-ray diffraction [WAXD; Phillips X’pert Pro MPD diffractometer with Cu–Kα (λ = 0.15418 nm)] was further used to characterize the crystal form and crystallinity. The 2θ scanning range was 10–30° with the rate of 3 min−1. The overall crystallinity, Xc, was calculated according to the following equation [25]:
(2)Xc=∑Acryst∑Acryst+∑Aamorp,where Acryst and Aamorp are the fitted areas of crystal and amorphous regions, respectively.Small-angle X-ray scattering (SAXS) was performed at 4B9A, Beijing Synchrotron Radiation Facility (BSRF), using a Mar345 detector. The sample was mounted onto a stage at the beamline at a sample to detector distance of 1750 mm. The one-dimensional correlation functionK(z) can be derived from the scattering intensity distribution profile as follows [26–28]:
(3)Kz=∫0∞Iqcosqzdq∫0∞Iqdq.wherez denotes the drawing direction. It must be noted that no multiplication q2 to I(q) is performed because of the highly anisotropic orientation of the lamellar crystals in the sample investigated and no extension of I(q) to a higher angle is carried out.Fourier transform infrared spectroscopy (FTIR) was applied to characterize the orientation degree of the PP films according to the dichroic ratioD [29].
(4)D=A//A⊥,where A∥ is the absorption parallel and A⊥ is the absorption perpendicular to a specific reference axis at a specific wavenumber. The Herman orientation function of this vibration is obtained according to [29]:
(5)f=23cos2α−1∗D−1D+2.whereα is the angle between transition moment and polymer chain axis, and the α value of 18o was used. The orientation of the crystalline phase, fc, can be determined from the D at 998 cm−1. While the average orientation function, fav, is obtained from the D at 972 cm−1. The orientation of amorphous phase, fa, is calculated according to:
(6)fav=Xcfc+1−Xcfa,where Xc is the degree of crystallinity determined by WAXD.


## 3. Results and Discussion

### 3.1. Dielectric Properties

The dielectric properties of BOPP and UOPP films are shown in Figure1. It can be observed that the dielectric constants of BOPP and UOPP films are almost constant (~2.25 and 2.45, respectively) when the frequency is lower than 1×106 Hz, and the losses are <0.02%, suggesting that PP films are superior stable dielectrics. The permittivity and dielectric loss of homogeneous materials are mainly related to the dipole moment of materials [30, 31]. Therefore, it is reasonable that the manufacturing method and annealing have no obvious effect on the dielectric constant and loss.Figure 1
Permittivity and dielectric loss of the PP films. Permittivity of (a) BOPP and (b) UOPP. Dielectric loss of (c) BOPP and (d) UOPP.
(a)(b)(c)(d)


### 3.2. Electric Breakdown Strength

The electric breakdown strength of PP films was determined and fitted with a two-parameter Weibull distribution function:PE=1−expE/Ebβ, where P(E) is the cumulative probability of the electric breakdown failure, E is the experimental electrical strength, Eb is the scale parameter, which means the breakdown strength at a cumulative failure probability of 63.2% and can be referred to as the characteristic breakdown strength of the dielectrics. The shape parameter β shows the dispersion of E data and the quality of film dielectrics [32, 33]. Figures 2(a) and 2(b) show the Weibull distribution of the PP films. The shape parameters β are about 10.0 and 8.5 for the BOPP films and UOPP films, respectively, suggesting a narrow dispersion of E data. Figures 2(c) and 2(d) show the Eb of PP films at different Ta. The Eb of initial BOPP film is 724.9 kV mm−1. After annealed at 100°C for 1 hour, there is no obvious change in the Eb. When Ta is increased to 110°C, Eb decreases to about 712.5 kV mm−1. Further increasing Ta leads to a gradual decrease of Eb. When Ta is higher than 140°C, an obvious decrease in the Eb can be observed. It can be concluded that Eb decreases with Ta for the BOPP films. For the UOPP films, quite different trend is observed. The Eb of initial UOPP film is 478.4 kV mm−1, much lower than that of initial BOPP film. After annealed at 100°C for 1hour, Eb increases to about 480.8 kV mm−1. Further increasing Ta leads to a gradual increase of Eb to 578.7 kV mm−1. When the Ta is higher than 140°C, an obvious decrease in the Eb can also be observed. The obvious decrease of Eb in both kinds of PP films can be attributed to the partial melting of PP crystals at temperature higher than 140°C. When Ta is lower than 140°C, Eb of the BOPP film decreases with the increase in Ta, while that of UOPP film shows a quite different trend. The different effects of annealing on Eb should originate from different microstructure evolutions.Figure 2
Weibull distribution and theEb of PP films. Weibull distribution of (a) BOPP films and (b) UOPP films. Eb of (c) BOPP films and (d) UOPP films.
(a)(b)(c)(d)


### 3.3. Thermal Analysis

The PP films were characterized with DSC as shown in Figure3. The initial BOPP film has two melting peaks, one at 164.5°C and the other at 170.9°C as shown in Figure 3(a). As the BOPP film was annealed at 100°C, a shoulder peak appears at 161.1°C, which gradually shifts to higher temperature and merges with the peak at 164.5°C at higher Ta. The shoulder peaks at about 161.1°C can be attributed to the melting of crystals formed at Ta, since they increase with Ta. While the peak at 164.5°C can be assigned to the melting of crystals from recrystallization. The peak at 170.9°C is much higher than the melting point of α form PP crystals (~163–167°C), which does not shift with Ta. Therefore, it is supposed that this melting peak should originate from the crystals with special microstructure. The industrially produced BOPP films have been stretched at large ratios (5.0×8.0) with the heat setting process to control the film shrinkage ratio. Therefore, there should exist a more stable microstructure that cannot be affected during the DSC heat scan. When polymers were stretched at a large ratio, fibril crystals may form. Different from the folding chain crystals, the fibril crystals have the properties of extend chain crystals with a melting point approaching the equilibrium melting point. The equilibrium melting point of PP α form crystal is ~186°C [34]. As a result, it is deduced that the peak at 170.9°C may be attributed to the melting of fibril crystals with partially extended chain segments [35]. Estimated from the proportion of the peak at 170.9°C, it is supposed that a large number of fibril crystals exist in BOPP films due to high ratio stretching in the manufacturing process.Figure 3
DSC heating curves and crystallinity of PP films. DSC heating curves of (a) BOPP films and (b) UOPP films. Crystallinity of (c) BOPP films and (d) UOPP films (∆Hf0=165Jg−1).
(a)(b)(c)(d)The UOPP films show quite different thermal behavior from that of BOPP films as shown in Figure3(b). The initial UOPP film has a melting peak at 166.3°C. After the UOPP film was annealed at 100°C, another melting peak appears at 163.6°C. Meanwhile, the melting peak at 163.6°C shifts to higher temperature and merges with the peak at 166.3°C, forming a shoulder peak on the left. According to the mechanism of lamellar thickening during high temperature annealing, the higher the Ta, the thicker the lamellae, the higher the melting temperature. The shoulder peak on the left side should originate from melting crystals formed at Ta, which may be attributed to the microcrystal form in the amorphous between the primary crystals [23]. For all UOPP films, the melting peak at 166.3°C does not change with the Ta. Since melting and recrystallization can easily take place during heating, the peak at 166.3°C may be attributed to the melting of crystals from recrystallization [36]. To make sure that the different melting behavior is due to various manufacturing processes but not the raw material, the second DSC heating scan for both BOPP and UOPP were carried out. As shown in Figure S1, after eliminating thermal history, both PP resins show two melting peaks, that is, one at 148.7°C, another at 163.3°C, which indicates that PP resin with similar chain structure and composition has been used, and the different melting behavior of BOPP and UOPP films is originated from the difference in the manufacturing process.The crystallinity was calculated using the melting enthalpy. The crystallinity of the initial BOPP film is 57.2%, which does not change when annealed at 100°C. AsTa is higher than 100°C, a gradual increase in crystallinity with Ta is observed, which changes greatly as the temperature is higher than 140°C. The highest crystallinity reaches 64.7% when annealed at 150°C. The crystallinity of initial UOPP film is about 52.5%. A large increase is observed as Ta is 110°C, and the highest crystallinity is 62.0% when annealed at 150°C. The crystallinity of the UOPP films is low, and it increases in a different manner compared with the BOPP films, which can be attributed to different manufacturing processes.


### 3.4. Wide-Angel X-Ray Diffraction

Figures4(a) and 4(b) show the WAXD profiles of the PP films. The peaks at 2θ angles of 14.1, 16.9, 18.6, and 25.7° can be assigned to the reflection peaks of (110), (040), (130), and (060) of α-form, respectively. The crystallinity was calculated after separating the amorphous phase, and the results are shown in Figures 4(c) and 4(d). The crystallinity of both kinds of films increases with Ta. For BOPP films, the crystallinity of the initial film is about 65.5%. The highest crystallinity of 70.0% is obtained at 150°C. While for UOPP films, the crystallinity of the initial film is about 64.7%, lower than that of BOPP film. The values increase sharply with Ta. The highest crystallinity of 75.8% is obtained at 150°C. The crystallinity obtained by DSC and WAXD shows the same trend of increasing with Ta, but in a different manner. Melting and recrystallization during the DSC heating scan may be the factor leading to the difference. When comparing Figure 2(c) with Figure 4(c), it can be observed that the crystallization and Eb of BOPP films change in an opposite trend. The initial BOPP film has the highest Eb, while the crystallinity is the lowest. After annealing at 100°C, slightly decreased Eb with a slightly increased crystallinity is observed. The slightly increase in crystallinity may be due to the relaxation and crystallization of low-molecular-weight fraction. As Ta is in the range of 110–140°C, Eb declines gradually, while the crystallinity increases slowly. The increase in Ta may have resulted in the partial melting and recrystallization, leading to the re-organization of crystals. As Ta is 150°C, a temperature near the melting point, the melting recrystallization and crystal re-organization should be more intense during annealing, and Eb decreases sharply. The comparison implies that the crystal structure change due to annealing will weaken the Eb of BOPP film. When comparing Figure 2(d) with Figure 4(d), both Eb and crystallinity of UOPP films increase with Ta, as Ta is lower than 140°C, which suggests that annealing favors strengthening the Eb of the UOPP film. As Ta is 150°C, the crystallinity reaches the highest, while Eb also decreases sharply, indicating the collapse of oriented crystal structure. The Eb and crystallinity of BOPP and UOPP films change in different ways with Ta, which suggests that crystallinity is not the determining factor affecting Eb.Figure 4
WAXD profiles and crystallinity of PP films. WAXD profiles of (a) BOPP films and (b) UOPP films. Crystallinity of (c) BOPP films and (d) UOPP films.
(a)(b)(c)(d)


### 3.5. Small-Angle X-Ray Scattering

SAXS was used to explore the effect of annealing on the microstructure of PP films. The typical 2D SAXS pattern of the BOPP and UOPP initial films are displayed in Figure5. The initial BOPP film has an oblate pattern, indicating that the orientation in the traverse direction is larger than the machine direction (MD). After annealing at 130°C, there is no significant change in the shape of the SAXS pattern when compared with the diagrams of initial films, whereas the UOPP film shows a typical uniaxial orientation pattern. The weak meridional streak in SAXS patterns is attributed to the shish-like crystals such as extended chain crystal structures and row nuclei in MD, while the appearance of strong equatorial maxima is attributed to kebab-like lamellar stacks, oriented perpendicularly to the MD [37]. After annealing at 130°C, the scattering intensity of both the shish-like and kebab-like crystals increases obviously. The morphologies of both BOPP and UOPP films after annealed at 130°C were observed with atomic force microscopy as shown in Figure S2. Crystals with no obvious orientation are observed in the BOPP film [Figure S2(a)], while parallel lamellar stacks are seen in the UOPP film [Figure S2(b)], which accords well with the 2D SAXS pattern.Figure 5
Small-angle X-ray scattering patterns of the PP films: (a) initial BOPP film, (b) BOPP film after annealed at 130°C, (c) initial UOPP film, and (d) UOPP film after annealed at 130°C.The one-dimensional scattering intensity distributions of the BOPP films along the MD direction are shown in Figure6(a). A much stronger increase in intensity is observed as Ta is higher than 130°C, indicating crystal perfection with the increase of the electron density difference between the lamellar crystals and amorphous layers. The one-dimensional correlation function derived from the scattering intensity distribution profile is shown in Figure 6(c). When the crystallinity is larger than 50%, the average thickness of the amorphous layer (da) and long period of lamellar stacks (dac) can be directly obtained from the correlation function [Figure 6(c)] [27]. The average da, dac, and average thickness of crystals (dc) values of BOPP films are shown in Figure 6(e). The initial da, dc, and dac values of the initial BOPP film are 4.2, 13.9 and 18.1 nm, respectively, which keeps almost stable as Ta is lower than 120°C. Obvious lamellar thickening appears as Ta is higher than 120°C, which can be attributed to the partial melting of unstable crystals followed by the structural re-organization during annealing at high temperatures.Figure 6
One-dimensional scattering intensity distribution profiles taken along the MD direction (a) and (b), the corresponding correlation functions (c) and (d), long periodicity, lamellar thickness, and the average thickness of the amorphous layer (e) and (f) at different annealing temperatures.
(a)(b)(c)(d)(e)(f)The one-dimensional scattering intensity distributions of UOPP films along the MD direction are shown in Figure6(b). It can be observed that the scattering peak shifts to smaller scattering vector q values with stronger intensity with the increase in Ta, which is the evidence of crystal perfection with the re-arrangement of lamellae and/or amorphous parts, resulting in an increase of the long periodicity and the electron density difference between the lamellar crystals and amorphous layers. The resultant correlation functions are shown in Figure 6(d). The average da, dc, and dac values of UOPP films are shown in Figure 6(f). Compared with the initial UOPP film, all the thicknesses increase with the increase in Ta. The increase in thickness can be assigned to volume expansion, the crystallization of amorphous part and re-organization of lamellar crystals by lamellar thickening. Compared with da, dc and dac increase in a much higher rate, especially when Ta is higher than 130°C, suggesting the lamellar thickening with the rise of Ta. The average da values of both the initial UOPP and BOPP films are at the same level, while the dc values are quite different, which can be attributed to the different film manufacturing process. The initial UOPP film is prepared using high-speed melt elongation, followed by quenching, resulting in imperfect crystals with small dc (~8.1 nm). While the BOPP film is made by biaxially stretching followed by heat setting near the melting temperature, high temperature heat setting leading to more stable crystals with much higher dc (~13.9 nm). The initial size and stability of the crystals in the initial films are quite different, so annealing has different effects on the structure evolution of two kinds of PP films. The dc increases with Ta, while Eb varies in a different trend [Figures 2(c) and 2(d) and 6(e) and 6(f)], which implies that long period of lamellar stacks or lamellar thickness variation cannot be directly correlated with Eb.


### 3.6. Fourier Transform Infrared Spectroscopy

The polarized FTIR spectra of polypropylene are shown in Figures7(a) and 7(b). The absorption at the wavenumber of 998 cm−1 is attributed to the crystalline phase (c-axis) while absorption at the wavenumber of 972 cm−1 is due to the contribution of both crystalline and amorphous phases [38]. The Herman orientation function was calculated according to the dichroic ratio as shown in Figures 7(c) and 7(d). For the BOPP films, fc decreases slowly while fa decreases fast with the rise of Ta first, which suggests that the amorphous chain segments relax faster than those in the crystal. As Ta is higher than 130°C, fc reduces in a much rapid rate, indicating re-organization of crystals. For the UOPP films, fc and fa almost keep stable below 110°C. As Ta is further increased, the orientations of the amorphous part and the crystal increase. Since the UOPP film consists of shish-kebab lamellae, that is, minor shish-like crystals growing along MD and a large number of kebab-like crystals oriented along the traverse direction, the increase in the orientation degree indicates that chain segments pack along MD during the lamellar re-organization. As Ta is higher than 140°C, the orientation degree falls down suggesting the collapse of the uniaxial orientation structure, which should be the upper limit application temperature for the UOPP film. When comparing Figure 2(c) with Figure 7(c), it can be observed that the initial BOPP film has the highest Eb and orientation degree. As Ta is increased to a temperature lower than 120°C, fa declines faster than, which may suggest that the decrease of Eb may mainly originate from the decrease of fa. As Ta is further increased to temperature lower than 140°C, fc declines faster than fa, implying the decrease of Eb may be due to the relaxation of fc as a result of melting and recrystallization. As Ta is 150°C, fc declines sharply, indicating obvious melting has led to the structure collapse of BOPP film, so Eb has the lowest value. For the UOPP film, both fc and Eb increase with Ta, as Ta is lower than 140°C. As Ta is 150°C, both fc and Eb fall. The orientation degree of both BOPP and UOPP films can correlate with Eb very well, suggesting that the orientation degree is highly correlated with the Eb of PP films. But linear correlation is not observed (Figure S1), since the crystallinity also has great influence on Eb [39]. Uniaxial orientation endows larger anisotropy to the films than biaxial orientation (Figure 5), so it seems that orientation degree is not feasible for comparison between different types of PP films. BOPP film has been stretched at large ratios (5.0×8.0) at both MD and traverse direction. Although the orientation degree of BOPP film is smaller, the chain segments orientation should be much larger than those of the UOPP film. Eb of BOPP film is much larger than that of UOPP film [Figures 2(c) and 2(d)], suggesting that microscopic chain segment orientation plays a more important role in Eb than the macroscopic orientation of lamellar stacks. Due to much higher Eb, BOPP film is the best choice for metallized PP film capacitor. When metallized PP film capacitor is thermally aged or self-healing after locally electric breakdown, the performance deterioration may result from chain segment re-organization, especially the decrease in orientation degree after experiencing high temperature.Figure 7
Polarized FTIR spectra of (a) BOPP and (b) UOPP films. Changes in the orientation function withTa for (c) BOPP and (d) UOPP films.
(a)(b)(c)(d)


## 3.1. Dielectric Properties

The dielectric properties of BOPP and UOPP films are shown in Figure1. It can be observed that the dielectric constants of BOPP and UOPP films are almost constant (~2.25 and 2.45, respectively) when the frequency is lower than 1×106 Hz, and the losses are <0.02%, suggesting that PP films are superior stable dielectrics. The permittivity and dielectric loss of homogeneous materials are mainly related to the dipole moment of materials [30, 31]. Therefore, it is reasonable that the manufacturing method and annealing have no obvious effect on the dielectric constant and loss.Figure 1
Permittivity and dielectric loss of the PP films. Permittivity of (a) BOPP and (b) UOPP. Dielectric loss of (c) BOPP and (d) UOPP.
(a)(b)(c)(d)


## 3.2. Electric Breakdown Strength

The electric breakdown strength of PP films was determined and fitted with a two-parameter Weibull distribution function:PE=1−expE/Ebβ, where P(E) is the cumulative probability of the electric breakdown failure, E is the experimental electrical strength, Eb is the scale parameter, which means the breakdown strength at a cumulative failure probability of 63.2% and can be referred to as the characteristic breakdown strength of the dielectrics. The shape parameter β shows the dispersion of E data and the quality of film dielectrics [32, 33]. Figures 2(a) and 2(b) show the Weibull distribution of the PP films. The shape parameters β are about 10.0 and 8.5 for the BOPP films and UOPP films, respectively, suggesting a narrow dispersion of E data. Figures 2(c) and 2(d) show the Eb of PP films at different Ta. The Eb of initial BOPP film is 724.9 kV mm−1. After annealed at 100°C for 1 hour, there is no obvious change in the Eb. When Ta is increased to 110°C, Eb decreases to about 712.5 kV mm−1. Further increasing Ta leads to a gradual decrease of Eb. When Ta is higher than 140°C, an obvious decrease in the Eb can be observed. It can be concluded that Eb decreases with Ta for the BOPP films. For the UOPP films, quite different trend is observed. The Eb of initial UOPP film is 478.4 kV mm−1, much lower than that of initial BOPP film. After annealed at 100°C for 1hour, Eb increases to about 480.8 kV mm−1. Further increasing Ta leads to a gradual increase of Eb to 578.7 kV mm−1. When the Ta is higher than 140°C, an obvious decrease in the Eb can also be observed. The obvious decrease of Eb in both kinds of PP films can be attributed to the partial melting of PP crystals at temperature higher than 140°C. When Ta is lower than 140°C, Eb of the BOPP film decreases with the increase in Ta, while that of UOPP film shows a quite different trend. The different effects of annealing on Eb should originate from different microstructure evolutions.Figure 2
Weibull distribution and theEb of PP films. Weibull distribution of (a) BOPP films and (b) UOPP films. Eb of (c) BOPP films and (d) UOPP films.
(a)(b)(c)(d)


## 3.3. Thermal Analysis

The PP films were characterized with DSC as shown in Figure3. The initial BOPP film has two melting peaks, one at 164.5°C and the other at 170.9°C as shown in Figure 3(a). As the BOPP film was annealed at 100°C, a shoulder peak appears at 161.1°C, which gradually shifts to higher temperature and merges with the peak at 164.5°C at higher Ta. The shoulder peaks at about 161.1°C can be attributed to the melting of crystals formed at Ta, since they increase with Ta. While the peak at 164.5°C can be assigned to the melting of crystals from recrystallization. The peak at 170.9°C is much higher than the melting point of α form PP crystals (~163–167°C), which does not shift with Ta. Therefore, it is supposed that this melting peak should originate from the crystals with special microstructure. The industrially produced BOPP films have been stretched at large ratios (5.0×8.0) with the heat setting process to control the film shrinkage ratio. Therefore, there should exist a more stable microstructure that cannot be affected during the DSC heat scan. When polymers were stretched at a large ratio, fibril crystals may form. Different from the folding chain crystals, the fibril crystals have the properties of extend chain crystals with a melting point approaching the equilibrium melting point. The equilibrium melting point of PP α form crystal is ~186°C [34]. As a result, it is deduced that the peak at 170.9°C may be attributed to the melting of fibril crystals with partially extended chain segments [35]. Estimated from the proportion of the peak at 170.9°C, it is supposed that a large number of fibril crystals exist in BOPP films due to high ratio stretching in the manufacturing process.Figure 3
DSC heating curves and crystallinity of PP films. DSC heating curves of (a) BOPP films and (b) UOPP films. Crystallinity of (c) BOPP films and (d) UOPP films (∆Hf0=165Jg−1).
(a)(b)(c)(d)The UOPP films show quite different thermal behavior from that of BOPP films as shown in Figure3(b). The initial UOPP film has a melting peak at 166.3°C. After the UOPP film was annealed at 100°C, another melting peak appears at 163.6°C. Meanwhile, the melting peak at 163.6°C shifts to higher temperature and merges with the peak at 166.3°C, forming a shoulder peak on the left. According to the mechanism of lamellar thickening during high temperature annealing, the higher the Ta, the thicker the lamellae, the higher the melting temperature. The shoulder peak on the left side should originate from melting crystals formed at Ta, which may be attributed to the microcrystal form in the amorphous between the primary crystals [23]. For all UOPP films, the melting peak at 166.3°C does not change with the Ta. Since melting and recrystallization can easily take place during heating, the peak at 166.3°C may be attributed to the melting of crystals from recrystallization [36]. To make sure that the different melting behavior is due to various manufacturing processes but not the raw material, the second DSC heating scan for both BOPP and UOPP were carried out. As shown in Figure S1, after eliminating thermal history, both PP resins show two melting peaks, that is, one at 148.7°C, another at 163.3°C, which indicates that PP resin with similar chain structure and composition has been used, and the different melting behavior of BOPP and UOPP films is originated from the difference in the manufacturing process.The crystallinity was calculated using the melting enthalpy. The crystallinity of the initial BOPP film is 57.2%, which does not change when annealed at 100°C. AsTa is higher than 100°C, a gradual increase in crystallinity with Ta is observed, which changes greatly as the temperature is higher than 140°C. The highest crystallinity reaches 64.7% when annealed at 150°C. The crystallinity of initial UOPP film is about 52.5%. A large increase is observed as Ta is 110°C, and the highest crystallinity is 62.0% when annealed at 150°C. The crystallinity of the UOPP films is low, and it increases in a different manner compared with the BOPP films, which can be attributed to different manufacturing processes.


## 3.4. Wide-Angel X-Ray Diffraction

Figures4(a) and 4(b) show the WAXD profiles of the PP films. The peaks at 2θ angles of 14.1, 16.9, 18.6, and 25.7° can be assigned to the reflection peaks of (110), (040), (130), and (060) of α-form, respectively. The crystallinity was calculated after separating the amorphous phase, and the results are shown in Figures 4(c) and 4(d). The crystallinity of both kinds of films increases with Ta. For BOPP films, the crystallinity of the initial film is about 65.5%. The highest crystallinity of 70.0% is obtained at 150°C. While for UOPP films, the crystallinity of the initial film is about 64.7%, lower than that of BOPP film. The values increase sharply with Ta. The highest crystallinity of 75.8% is obtained at 150°C. The crystallinity obtained by DSC and WAXD shows the same trend of increasing with Ta, but in a different manner. Melting and recrystallization during the DSC heating scan may be the factor leading to the difference. When comparing Figure 2(c) with Figure 4(c), it can be observed that the crystallization and Eb of BOPP films change in an opposite trend. The initial BOPP film has the highest Eb, while the crystallinity is the lowest. After annealing at 100°C, slightly decreased Eb with a slightly increased crystallinity is observed. The slightly increase in crystallinity may be due to the relaxation and crystallization of low-molecular-weight fraction. As Ta is in the range of 110–140°C, Eb declines gradually, while the crystallinity increases slowly. The increase in Ta may have resulted in the partial melting and recrystallization, leading to the re-organization of crystals. As Ta is 150°C, a temperature near the melting point, the melting recrystallization and crystal re-organization should be more intense during annealing, and Eb decreases sharply. The comparison implies that the crystal structure change due to annealing will weaken the Eb of BOPP film. When comparing Figure 2(d) with Figure 4(d), both Eb and crystallinity of UOPP films increase with Ta, as Ta is lower than 140°C, which suggests that annealing favors strengthening the Eb of the UOPP film. As Ta is 150°C, the crystallinity reaches the highest, while Eb also decreases sharply, indicating the collapse of oriented crystal structure. The Eb and crystallinity of BOPP and UOPP films change in different ways with Ta, which suggests that crystallinity is not the determining factor affecting Eb.Figure 4
WAXD profiles and crystallinity of PP films. WAXD profiles of (a) BOPP films and (b) UOPP films. Crystallinity of (c) BOPP films and (d) UOPP films.
(a)(b)(c)(d)


## 3.5. Small-Angle X-Ray Scattering

SAXS was used to explore the effect of annealing on the microstructure of PP films. The typical 2D SAXS pattern of the BOPP and UOPP initial films are displayed in Figure5. The initial BOPP film has an oblate pattern, indicating that the orientation in the traverse direction is larger than the machine direction (MD). After annealing at 130°C, there is no significant change in the shape of the SAXS pattern when compared with the diagrams of initial films, whereas the UOPP film shows a typical uniaxial orientation pattern. The weak meridional streak in SAXS patterns is attributed to the shish-like crystals such as extended chain crystal structures and row nuclei in MD, while the appearance of strong equatorial maxima is attributed to kebab-like lamellar stacks, oriented perpendicularly to the MD [37]. After annealing at 130°C, the scattering intensity of both the shish-like and kebab-like crystals increases obviously. The morphologies of both BOPP and UOPP films after annealed at 130°C were observed with atomic force microscopy as shown in Figure S2. Crystals with no obvious orientation are observed in the BOPP film [Figure S2(a)], while parallel lamellar stacks are seen in the UOPP film [Figure S2(b)], which accords well with the 2D SAXS pattern.Figure 5
Small-angle X-ray scattering patterns of the PP films: (a) initial BOPP film, (b) BOPP film after annealed at 130°C, (c) initial UOPP film, and (d) UOPP film after annealed at 130°C.The one-dimensional scattering intensity distributions of the BOPP films along the MD direction are shown in Figure6(a). A much stronger increase in intensity is observed as Ta is higher than 130°C, indicating crystal perfection with the increase of the electron density difference between the lamellar crystals and amorphous layers. The one-dimensional correlation function derived from the scattering intensity distribution profile is shown in Figure 6(c). When the crystallinity is larger than 50%, the average thickness of the amorphous layer (da) and long period of lamellar stacks (dac) can be directly obtained from the correlation function [Figure 6(c)] [27]. The average da, dac, and average thickness of crystals (dc) values of BOPP films are shown in Figure 6(e). The initial da, dc, and dac values of the initial BOPP film are 4.2, 13.9 and 18.1 nm, respectively, which keeps almost stable as Ta is lower than 120°C. Obvious lamellar thickening appears as Ta is higher than 120°C, which can be attributed to the partial melting of unstable crystals followed by the structural re-organization during annealing at high temperatures.Figure 6
One-dimensional scattering intensity distribution profiles taken along the MD direction (a) and (b), the corresponding correlation functions (c) and (d), long periodicity, lamellar thickness, and the average thickness of the amorphous layer (e) and (f) at different annealing temperatures.
(a)(b)(c)(d)(e)(f)The one-dimensional scattering intensity distributions of UOPP films along the MD direction are shown in Figure6(b). It can be observed that the scattering peak shifts to smaller scattering vector q values with stronger intensity with the increase in Ta, which is the evidence of crystal perfection with the re-arrangement of lamellae and/or amorphous parts, resulting in an increase of the long periodicity and the electron density difference between the lamellar crystals and amorphous layers. The resultant correlation functions are shown in Figure 6(d). The average da, dc, and dac values of UOPP films are shown in Figure 6(f). Compared with the initial UOPP film, all the thicknesses increase with the increase in Ta. The increase in thickness can be assigned to volume expansion, the crystallization of amorphous part and re-organization of lamellar crystals by lamellar thickening. Compared with da, dc and dac increase in a much higher rate, especially when Ta is higher than 130°C, suggesting the lamellar thickening with the rise of Ta. The average da values of both the initial UOPP and BOPP films are at the same level, while the dc values are quite different, which can be attributed to the different film manufacturing process. The initial UOPP film is prepared using high-speed melt elongation, followed by quenching, resulting in imperfect crystals with small dc (~8.1 nm). While the BOPP film is made by biaxially stretching followed by heat setting near the melting temperature, high temperature heat setting leading to more stable crystals with much higher dc (~13.9 nm). The initial size and stability of the crystals in the initial films are quite different, so annealing has different effects on the structure evolution of two kinds of PP films. The dc increases with Ta, while Eb varies in a different trend [Figures 2(c) and 2(d) and 6(e) and 6(f)], which implies that long period of lamellar stacks or lamellar thickness variation cannot be directly correlated with Eb.


## 3.6. Fourier Transform Infrared Spectroscopy

The polarized FTIR spectra of polypropylene are shown in Figures7(a) and 7(b). The absorption at the wavenumber of 998 cm−1 is attributed to the crystalline phase (c-axis) while absorption at the wavenumber of 972 cm−1 is due to the contribution of both crystalline and amorphous phases [38]. The Herman orientation function was calculated according to the dichroic ratio as shown in Figures 7(c) and 7(d). For the BOPP films, fc decreases slowly while fa decreases fast with the rise of Ta first, which suggests that the amorphous chain segments relax faster than those in the crystal. As Ta is higher than 130°C, fc reduces in a much rapid rate, indicating re-organization of crystals. For the UOPP films, fc and fa almost keep stable below 110°C. As Ta is further increased, the orientations of the amorphous part and the crystal increase. Since the UOPP film consists of shish-kebab lamellae, that is, minor shish-like crystals growing along MD and a large number of kebab-like crystals oriented along the traverse direction, the increase in the orientation degree indicates that chain segments pack along MD during the lamellar re-organization. As Ta is higher than 140°C, the orientation degree falls down suggesting the collapse of the uniaxial orientation structure, which should be the upper limit application temperature for the UOPP film. When comparing Figure 2(c) with Figure 7(c), it can be observed that the initial BOPP film has the highest Eb and orientation degree. As Ta is increased to a temperature lower than 120°C, fa declines faster than, which may suggest that the decrease of Eb may mainly originate from the decrease of fa. As Ta is further increased to temperature lower than 140°C, fc declines faster than fa, implying the decrease of Eb may be due to the relaxation of fc as a result of melting and recrystallization. As Ta is 150°C, fc declines sharply, indicating obvious melting has led to the structure collapse of BOPP film, so Eb has the lowest value. For the UOPP film, both fc and Eb increase with Ta, as Ta is lower than 140°C. As Ta is 150°C, both fc and Eb fall. The orientation degree of both BOPP and UOPP films can correlate with Eb very well, suggesting that the orientation degree is highly correlated with the Eb of PP films. But linear correlation is not observed (Figure S1), since the crystallinity also has great influence on Eb [39]. Uniaxial orientation endows larger anisotropy to the films than biaxial orientation (Figure 5), so it seems that orientation degree is not feasible for comparison between different types of PP films. BOPP film has been stretched at large ratios (5.0×8.0) at both MD and traverse direction. Although the orientation degree of BOPP film is smaller, the chain segments orientation should be much larger than those of the UOPP film. Eb of BOPP film is much larger than that of UOPP film [Figures 2(c) and 2(d)], suggesting that microscopic chain segment orientation plays a more important role in Eb than the macroscopic orientation of lamellar stacks. Due to much higher Eb, BOPP film is the best choice for metallized PP film capacitor. When metallized PP film capacitor is thermally aged or self-healing after locally electric breakdown, the performance deterioration may result from chain segment re-organization, especially the decrease in orientation degree after experiencing high temperature.Figure 7
Polarized FTIR spectra of (a) BOPP and (b) UOPP films. Changes in the orientation function withTa for (c) BOPP and (d) UOPP films.
(a)(b)(c)(d)


## 4. Conclusion

BOPP and UOPP films were annealed, and the electric performance and structure evolution had been investigated. The BOPP films have high initialEb, which decreases with Ta. The UOPP films have low initial Eb, which increases first and then decreases with Ta. In BOPP films, there exist a large number of fibril crystals with larger lamellar thickness and higher melting temperature. While in UOPP films, folded chain crystals are the main crystal species. The crystallinity of both films rises with Ta, and obvious lamellar thickening takes place after 130°C. The orientation degree and Eb show similar trend with Ta for both BOPP and UOPP films, suggesting that orientation degree is highly correlated with the Eb. Higher Eb of BOPP films can be attributed to larger lamellar thickness and higher orientation of chain segments. The performance deterioration of metallized PP film capacitors after aging or experiencing local high temperature may result from the decrease in the orientation degree of the BOPP film.



---

*Source: 5970484-2022-11-08.xml*