Materials Science & Engineering B 259 (2020) 114605

Contents lists available at ScienceDirect

Materials Science & Engineering B

journal homepage: www.elsevier.com/locate/mseb

Manufacture of biaxially-oriented polyamide 6 (BOPA6) films with high T

transparencies, mechanical performances, thermal resistance, and gas
blocking capabilities
Lung-Chang Liua, Chiu-Chun Laib, , Min-Tsung Lua, Chih-Hung Wua, Chien-Ming Chena
⁎

a
Material and Chemical Research Laboratories, Industrial Technology Research Institute, Hsinchu 30011, Taiwan, ROC
b
Department of Textile Engineering, Chinese Culture University, Taipei 11114, Taiwan, ROC

ARTICLE INFO ABSTRACT

Keywords: Polyamide 6 (PA 6) with different relative viscosities (RV) have been prepared and their thermal, rheological as
Polyamide 6 well as crystallization properties are highly dependent on their RV. Since PA 6 with RV of 3.16 exhibits the
Physical property highest crystallization speed, it has been subsequently extrusion-molded to give lab-made PA 6 film. After
Biaxially stretch biaxially stretched, lab-made biaxially-oriented PA 6 (BOPA6) films have eventually manufactured.
Biaxially-oriented polyamide
Experimental results represent that lab-made BOPA6 film with biaxially stretching ratio of 300% performs su-
Electrical encapsulation
Food package
perior physical properties to lab-made PA 6 film and commercial Unitika ON-15, proving that it is a highly
potential polymeric film for electrical encapsulation and food packages.

1. Introduction After extrusion-molded with PA 6, lab-made PA 6 film has been man-

Polyamide 6 (i.e. PA 6 or Nylon 6) is a well-known engineering
plastic and has attracted much attention because of its excellent me-
chanical strengths [1], extraordinary abrasion resistance [2], good
processibilities [3], high thermal stabilities [4], and miscellaneous ap-
plications such as bearing bushes [5], deep-sea pressure vessels [6],
gears [7], fabrics [8], wind turbines [9], light-emitting diodes [10],
electrochromic devices [11], fuel cells [12], bone tissue engineering
[13], solar cells [14], vehicles [15], smart windows [16], and so on.
However, the thermal resistance, mechanical properties, and gas
blocking capability of its film are not satisfactory when utilized for food
packages [17]. Since biaxially stretching procedure has been proved to
enhance the physical characteristics of polymers (e.g. polyethylene
terephthalate (PET) [18], polypropylene (PP) [19], polyethylene (PE)
[20], polyvinyl chloride (PVC) [21], polylactide (PLA) [22], etc.),
manufacture of biaxially-oriented PA 6 (i.e. BOPA6) films may meet the
physical requirements for food packages. Nonetheless, the research
with respect to this issue is rarely reported.
In this paper, we have prepared PA 6 with different relative visc-
osities (RV) and also explored their thermal characteristics, crystalline
properties, rheological performances, and crystal growth behaviors.
ufactured and then biaxially stretched to produce lab-made BOPA6
films with high transparencies, mechanical performances, thermal re-
sistance, and gas blocking capabilities. Experimental results elucidate
that
the physical properties (i.e. stress, shrinkage rate, glass transition
temperature, crystallinity, moisture/oxygen barrier performances, and
surface tension) of PA 6 film have been improved by the biaxially
stretching process and lab-made BOPA6 film is a highly potential film
for electrical encapsulation and food packages.
2. Experimental
2.1. Materials and instruments
Caprolactam (CPL; Fig. 1(a)) was obtained from Aldrich Co. and
used without further purification. All materials in this study were uti-
lized without further purification. The relative viscosity (RV), differ-
ential scanning calorimeter (DSC), and thermogravimetric analysis
(TGA) were measured with a Brookfield KV100 capillary viscometer in
formic acid at 25 °C, a Perkin Elmer DSC 7 at a heating/cooling rate of
5 °C/min under flowing nitrogen, and a Perkin Elmer TGA 7 at a

⁎
Corresponding author.
E-mail address: cclai168@yahoo.com (C.-C. Lai).

https://doi.org/10.1016/j.mseb.2020.114605
Received 7 March 2020; Accepted 16 June 2020
0921-5107/ © 2020 Elsevier B.V. All rights reserved.
L.-C. Liu, et al. Materials Science & Engineering B 259 (2020) 114605

Fig. 1. (a) Synthetic procedure of lab-made PA 6, (b) schematic presentation of utilized T-Die, (c) photograph of lab-made PA 6 film, (d) photograph of lab-made
BOPA film I, (e) photograph of lab-made BOPA film II, and (f) photograph of lab-made BOPA film III.

Table 1 heating rate of 20 °C/min under flowing nitrogen, respectively. More-

Physical properties of PA 6I-6V. over, we examined
Material RV Mwa Tmb Tcb Heat of Crystallinityc Tdd haze, transparency, mechanical properties (i.e. stress and strain),
(g/mole) (°C) (°C) fusionb (%) (°C) shrinkage rate, dynamic mechanical analysis (DMA), water vapor
(ΔHf) transmission rate (WVTR), oxygen transmission rate (OTR), surface
(J/g) tension, and thickness by a NDH-7000 at 25 °C, a HITACHI U-3300 at
PA 6I 2.42 15,965 225.1 178.0 94.54 49.8 392.1
25 °C, a JMT-UTS machine following ASTM D638, a FST-01 following
PA 6II 2.75 19,611 225.3 177.4 83.14 43.8 393.6 ASTM D2732, a TA Q500 at a heating rate of 10 °C/min under flowing
PA 6III 3.16 24,141 225.5 176.7 79.49 41.8 395.9 nitrogen, a PERMATRAN-W 3/61 following ASTM D3985-05, an ILLI-
PA 6IV 3.67 29,776 226.1 175.6 71.62 37.7 396.3 NOIS-8501 following ASTM E96, a DCA-100 Tensiometer following
PA 6V 4.03 33,754 226.5 174.6 65.20 36.6 398.5
ASTM D5946, and a surface profiler (TENCOR P-10), respectively.
a
Mw (weight-average molecular weight) was determined with the following
equation [24]: Mw = 11049RV 107736 where RV represented the relative 2.2. Preparation of lab-made PA 6, PA 6 films, and BOPA6 films
viscosity.
b
Melting temperature (Tm), crystallization temperature (Tc), and heat of
Lab-made PA 6 with distinct RV (i.e. PA 6I-6V) were prepared from
fusion (ΔHf) were determined with the DSC results.
c Hf ring-opening polymerization of CPL and characterized by the procedure
Crystallinity was defined as Crystallinity = × 100% where ΔHf100 re-
Hf 100 reported previously [23] as shown in Fig. 1(a). The details are described
presented the heat of fusion with 100% crystallinity. below. CPL were stirred at pH value of 7.5 by titration in the presence
d
Decomposition temperature (Td) was determined with the TGA result and of water and purified with active carbon powder at 25 °C. Then the
defined as the decomposition temperature at 5% weight loss. solution was heated at 220 °C and atmospheric pressure for 3 h,

2
L.-C. Liu, et al. Materials Science & Engineering B 259 (2020) 114605

Fig. 2. (a) DSC of PA 6I-6V with a heating rate of 5 °C/min, (b) DSC of PA 6I-6V with a cooling rate of 5 °C/min, (c) TGA of PA 6I-6V with a heating rate of 20 °C/
min, and (d) dependence of apparent shear viscosity on apparent shear rate for PA 6I-6V.

removing the water. After polymerized at 260 °C for 4,5,6,7, and 8 h
under vacuum of 4 × 10−6 Torr, PA 6I-6V was acquired, respectively.
Their physical properties were listed in Table 1.
PA 6III was subsequently extrusion-molded to produce lab-made PA
6 film with a twin-screw extruder (Brabender PL 2100; screw diameter:
25 mm, L/D ratio: 20) and a T-Die (Fig. 1(b)) at 240 °C and 3,500 r.p.m.
Afterwards, lab-made PA 6 film ((Fig. 1(c); length: 100 mm; width:
100 mm; thickness: 67 μm) was biaxially-stretched with to 200%,
300%, and 350% by a Bruckner KARO IV at 190 °C, then kept in this
form with clamps at 230 °C for 10 s, and eventually heated to 160 °C for
5 min to erase the previous thermal history, generating lab-made
BOPA6 film I (Fig. 1(d); length: 200 mm; width: 200 mm; thickness:
25 μm), lab-made BOPA6 film II (Fig. 1(e); length: 300 mm; width:
300 mm; thickness: 15 μm), and lab-made BOPA6 film III (Fig. 1(f);
length: 350 mm; width: 350 mm; thickness: 11 μm) .
3. Results and discussion
3.1. Physical performances of PA 6I-6V
As manifested in Table 1, thermal characteristics (viz. Tm (Fig. 2(a)),
Tc (Fig. 2(b)), and Td (Fig. 2(c))), crystalline behaviors (viz. crystal-
linity), and rheological properties (Fig. 2(d)) of PA 6I-6V are highly
dependent on Mw, which is proportional to RV [24] because PA 6 with
higher Mw exhibits higher rigidity and lower chain mobility, therefore
leading to higher Tm, Td as well as apparent shear viscosity and lower
Tc,ΔHf as well as crystallinity. To further investigate the crystallization
performances of PA 6I-6V, the Avrami equation (i.e. Eq. (1)) was uti-
lized for probing crystal growth morphology and crystallization growth
rate.

3
L.-C. Liu, et al. Materials Science & Engineering B 259 (2020) 114605

Fig. 3. DSC exotherms for isothermal crystallization of (a) PA 6I, (b) PA 6II, (c) PA 6III, (d) PA 6IV, and (e) PA 6V quickly cooled from the melt state to the given
temperatures for isothermal crystallization.

ln(1 X) = kt n (1) log( ln(1 X )) = n log t + log k (2)

where X, k, t, and n represent the crystallinity, Avrami constant, time, Hf

and Avrami exponent, respectively. X=
Hf 100 (3)
Eq. (2) is derived from Eq. (1), and X is given from the DSC exo-
therms for isothermal crystallization of PA 6I-6V (Fig. 3(a)–(e)) and Eq. where ΔHf and ΔHf100 represent the heat of fusion and the heat of fusion
(3): with 100% crystallinity, respectively [25].
The n and k are determined from the plot of log(−ln (1 − X)) (i.e.

4
L.-C. Liu, et al. Materials Science & Engineering B 259 (2020) 114605

Table 2 3.2. Physical characteristics of lab-made PA 6 films and BOPA6 films

Avrami exponent (n) and Avrami constant (k) of PA 6I-6V.
Material Isothermal crystallization As displayed in Table 3, introduction of biaxially stretching process
drastically meliorates the stress, shrinkage rate, glass transition tem-
Temperature n k t1/2 perature (Tg), crystallinity, WVTR, OTR as well as surface tension and
(°C) (min−n) (min) deteriorate the haze, transparency, strain as well as thickness since the
PA 6I 183 2.3 0.2367 1.58 haze, transparency, stress, strain, shrinkage, Tg, crystallinity, WVTR,
185 2.3 0.1503 1.93 OTR, surface tension, and thickness of lab-made BOPA6 film I are
187 2.3 0.0876 2.42 0.63%, 90.9%, 53.9 MPa, 26%, 0.7%, 100.3 °C, 24.2%, 531 g m−2
189 2.3 0.0523 3.09 day−1 atm−1, 98 m−2 day−1 atm−1, 49 mN/m, and 25 μm, respec-
PA 6II 183 2.3 0.2146 1.68 tively, while those of lab-made PA6 film are 0.16%, 91.3%, 31.9 MPa,
185 2.3 0.1291 2.09 189%, 1.0%, 95.9 °C, 20.5%, 901 g m−2 day−1 atm−1, 116 m−2 day−1
187 2.3 0.0743 2.65
atm−1, 58 mN/m, and 67 μm, respectively. This consequence originates
189 2.3 0.0469 3.30
from that higher film orientation and more crystallites lead to higher
PA 6III 183 2.3 0.3882 1.29
chain alignment, lower free volume, higher ordered configuration,
185 2.4 0.2376 1.58
187 2.4 0.13801 1.96 lower gas/optical penetration, and higher rigidity [26]. Nevertheless,
189 2.4 0.0842 2.40 the physical performances of lab-made BOPA6 film I cannot meet the
PA 6IV 183 2.4 0.1319 2.00
requirements of commercial BOPA6 film (i.e. Unitika ON-15), whose
185 2.4 0.0819 2.41 haze, transparency, stress, strain, shrinkage, Tg, crystallinity, WVTR,
187 2.4 0.0453 3.15 OTR, surface tension, and thickness are 2.93%, 90.5%, 72.3 MPa, 22%,
189 2.5 0.0227 3.94 0.5%, 101.2 °C, 30.5%, 260 g m−2 day−1 atm−1, 85 m−2 day−1 atm−1,
PA 6V 183 2.4 0.1145 2.18 36 mN/m, and 15 μm, respectively. In order to further promote the
185 2.4 0.0599 2.83 physical properties, biaxially stretching ratio has been enlarged from
187 2.4 0.0326 3.57
200% to 300%, obtaining lab-made BOPA6 film II, whose haze, trans-
189 2.5 0.0165 4.50
parency, stress, strain, shrinkage, Tg, crystallinity, WVTR, OTR, surface
tension, and thickness are 2.70, 90.2%, 73.5 MPa, 23%, 0.2%, 101.6 °C,
31.3%, 213 g m−2 day−1 atm−1, 68 m−2 day−1 atm−1, 34 mN/m, and
15 μm, respectively. For the sake of further heightening the physical
the ordinate) versus log t (i.e. the abscissa) since the slope and intercept characteristics, we have also tried to manufacture lab-made BOPA6 film
of plot are n and log k, respectively (Table 2). Experimental results III with biaxially stretching ratio of 350%. Nonetheless, as shown in
indicate that the n values of PA 6I-6V range within 2–3 (Table 2) and Fig. 1(f), lab-made BOPA6 film III is fractured. Experimental results
increase with Mw and crystallization temperature, revealing that both reveal that lab-made BOPA6 film II possesses better optical perme-
2D (i.e. plate) and 3D (i.e. spherulite) crystal growth morphology ability, higher mechanical strengths, greater dimensional stability,
produce when crystallized at 183–189 °C and high Mw as well as higher thermal resistance, lower gas barrier performances, higher
crystallization temperature facilitate the generation of spherulite. Ad- crystallinity, and lower surface tension than commercial Unitika ON-
ditionally, their k values decrease and their t1/2 (i.e. half-time of crys- 15, demonstrating that it is a highly potential electrical encapsulation
tallization) increase with the raise of crystallization temperature and and food-package film.
Mw owing to the reduction for degree of undercooling and chain mo-
bility, except PA 6III. Among all the lab-made PA 6, PA 6III exhibits the 4. Conclusions
highest k values and lowest t1/2 because the effect of entanglement
could surpass that of chain mobility in case of PA 6III, consequently In conclusion, we have researched the influence for RV of PA6 on its
resulting in the highest degree of undercooling [23]. Since PA 6III physical performances and prepared lab-made BOPA6 film II with high
possesses moderate thermal resistance, passable crystallinity, medium optical penetrability, good mechanical rigidity, low contractility, high
rheological performance, and the fastest crystallization rate, we have thermal stability, low gas permeation, high crystallinity, and low sur-
tried to apply it for BOPA6 films. face tension, being a promising film for electrical and food wrappings.

Table 3
Physical properties of lab-made PA6 film, lab-made BOPA6 films, and commercial BOPA6 film.
Material Haze Trans- Stress Strain Shrinkage rate Tga Cry- WVTR OTR Surface Thickness
(%) parency (MPa) (%) (%) (°C) stallinityb (g m−2 day−1 (g m−2 day−1 tension (μm)
(%) (%) atm−1) atm−1) (mN/m)

Lab-made PA6 film 0.16 91.3 31.9 189 1.0 95.9 20.5 901 116 58 67
Lab-made BOPA6 film I 0.63 90.9 53.9 26 0.7 100.3 24.2 531 98 49 25
Lab-made BOPA6 film II 2.70 90.2 73.5 23 0.2 101.6 31.3 213 68 34 15
Commercial BOPA6 film 2.93 90.5 72.3 22 0.5 101.2 30.5 260 85 36 15
(Unitika ON-15)

a
Glass transition temperature (Tg) was determined with the DMA results.
b
Crystallinity was defined as where ΔHf and ΔHf100 represented the heat of fusion with sample and 100% crystallinity, respectively. ΔHf was determined with the
DSC results.

5
L.-C. Liu, et al.
In the near future, lab-made BOPA6 film II will be applied for wide-
spread utilizations (e.g. optical films, touch panels, e-papers, lithium-
ion battery, light-emitting diodes, solar cells, etc.).
5. Data availability
The data used to support the findings of this study are available
from the corresponding author upon request.
References
[1] R. Hari, K.M. Mini, Mechanical and durability properties of sisal-Nylon 6 hybrid
fibre reinforced high strength SCC, Constr. Build. Mater. 204 (2019) 479–491.
[2] S. Kumar, K. Panneerselvam, Two-body abrasive wear behavior of Nylon 6 and glass
fiber reinforced (GFR) Nylon 6 composite, Proc. Technol. 25 (2016) 1129–1136.
[3] V.S. Balakrishnan, K. Wartig, N. Tsombanis, H. Seidlitz, Influence of processing
parameters on the impact behaviour of glass/polyamide-6 composite, Compos. Part
B 159 (2019) 292–299.
[4] J. Yu, G. Gröbner, B. Tonpheng, O. Andersson, Microstructure, nucleation and
thermal properties of high-pressure crystallized MWCNT/nylon-6 composites,
Polymer 52 (2011) 5521–5527.
[5] P.D. Neis, N.F. Ferreira, J.C. Poletto, J. Sukumaran, Y. Zhang, Tribological behavior
of polyamide-6 plastics and their potential use in industrial applications, Wear
376–377 (2017) 1391–1398.
[6] M. Arhant, C. Briancon, C. Burtin, P. Davies, Carbon/polyamide 6 thermoplastic
composite cylinders for deep sea applications, Compos. Struct. 212 (2019)
535–546.
[7] K. Mao, W. Li, C.J. Hooke, D. Walton, Friction and wear behaviour of acetal and
nylon gears, Wear 267 (2009) 639–645.
[8] W. Zhang, R.C. Tang, Adsorption and flame retardant properties of potassium di-
phenyl sulfonate on nylon 6 fabric, React. Funct. Polym. 126 (2018) 36–43.
[9] H.D. Pham, P. Cartraud, F. Schoefs, T. Soulard, C. Berhault, Dynamic modeling of
nylon mooring lines for a floating wind turbine, Appl. Ocean Res. 87 (2019) 1–8.
[10] R. Erdem, M. İlhan, M.K. Ekmekci, O. Erdem, Electrospinning, preparation and
photoluminescence properties of CoNb2O6:Dy3 ± incorporated polyamide 6 com-
posite fibers, Appl. Surf. Sci. 421 (2017) 240–246.
[11] J.R. Araujo, C.B. Adamo, M.A. De Paoli, Conductive composites of polyamide-6
with polyaniline coated vegetal fiber, Chem. Eng. J. 174 (2011) 425–431.
[12] J.K. Kuo, C.K. Chen, A novel Nylon-6–S316L fiber compound material for injection
Materials Science & Engineering B 259 (2020) 114605
molded PEM fuel cell bipolar plates, J. Power Sources 162 (2006) 207–214.
[13] H.R. Pant, P. Risal, C.H. Park, L.D. Tijing, Y.J. Jeong, C.S. Kim, Synthesis, char-
acterization, and mineralization of polyamide-6/calcium lactate composite nano-
fibers for bone tissue engineering, Colloids Surf. B 102 (2013) 152–157.
[14] Y. Cai, C. Gao, X. Xu, Z. Fu, X. Fei, Y. Zhao, Q. Chen, X. Liu, Q. Wei, G. He, H. Fong,
Electrospun ultrafine composite fibers consisting of lauric acid and polyamide 6 as
form-stable phase change materials for storage and retrieval of solar thermal en-
ergy, Solar Energy Mater. Solar Cells 103 (2012) 53–61.
[15] W. He, J. Gao, S. Liao, X. Wang, S. Qin, P. Song, A facile method to improve thermal
stability and flame retardancy of polyamide 6, Compos. Commun. 13 (2019)
143–150.
[16] W.R. Huang, Z. He, J.L. Wang, J.W. Liu, S.H. Yu, Mass production of nanowire-
Nylon flexible transparent smart windows for PM2.5 capture, iScience 12 (2019)
333–341.
[17] A. Agarwal, A. Raheja, T.S. Natarajan, T.S. Chandra, Effect of electrospun mon-
tmorillonite-nylon 6 nanofibrous membrane coated packaging on potato chips and
bread, Innov. Food Sci. Emerg. Technol. 26 (2014) 424–430.
[18] M.H. Chen, C.C. Lai, H.L. Chen, C.H. Lin, H.T. Hsiao, L.C. Liu, C.M. Chen,
Preparation of long-chain branched polyethylene terephthalates (PETs), and crys-
tallization behaviors, thermal characteristics, and hydrolysis resistance of their
biaxially stretching films, J. Phys. Chem. Solids 129 (2019) 354–367.
[19] I. Rytoluoto, A. Gitsas, S. Pasanen, K. Lahti, Effect of film structure and morphology
on the dielectric breakdown characteristics of cast and biaxially oriented poly-
propylene films, Euro. Polym. J. 95 (2017) 606–624.
[20] C. Wan, T. Cao, X. Chen, L. Meng, L. Li, Fabrication of polyethylene nanofibrous
membranes by biaxial stretching, Mater. Today Commun. 17 (2018) 24–30.
[21] A.S. Ognedal, A.H. Clausen, M. Polanco-Loria, A. Benallal, B. Raka,
O.S. Hopperstad, Experimental and numerical study on the behaviour of PVC and
HDPE in biaxial tension, Mech. Mater. 54 (2012) 18–31.
[22] S. Ouchiar, G. Stoclet, C. Cabaret, A. Addad, V. Gloaguen, Effect of biaxial
stretching on thermomechanical properties of polylactide based nanocomposites,
Polymer 99 (2016) 358–367.
[23] C.C. Lai, S.Y. Chen, M.H. Chen, H.L. Chen, H.T. Hsiao, L.C. Liu, C.M. Chen,
Preparation and characterization of heterocyclic polyamide 6 (PA 6) with high
transparencies and low hygroscopicities, J. Mol. Struct. 1175 (2019) 836–843.
[24] S.P. Rwei, P. Ranganathan, Y.H. Lee, Synthesis and characterization of low melting
point PA6 copolyamides from ε-caprolactam with bio-based polyamide salt, J. Mol.
Struct. 1186 (2019) 285–296.
[25] X.F. Lu, J.N. Hay, Isothermal crystallization kinetics and melting behaviour of poly
(ethylene terephthalate), Polymer 42 (2001) 9423–9431.
[26] W.D. Callister Jr., Materials Science and Engineering an Introduction, fourth ed.,
John Wiley & Sons, New York, 1997, pp. 456–460.