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Polyamides (Nylons)
8 Polyamides (Nylons) High-molecular-weight polyamides are commonly known as nylon. Polyamides are crystalline polymers typically produced by the condensation of a diacid and a diamine. There are several types and each type is often described by a number, such as nylon 66 or polyamide 66 (PA66). The numeric suffixes refer to the number of carbon atoms present in the molecular structures of the amine and acid, respectively (or a single suffix if the amine and acid groups are part of the same molecule). The polyamide plastic materials discussed in this book and the monomers used to make them are given in Table 8.1. The general reaction is shown in Fig. 8.1. The eCOOH acid group reacts with the NH2 amine group to form the amide. A molecule of water is given off as the nylon polymer is formed. The
properties of the polymer are determined by the R and R0 groups in the monomers. In nylon 6,6, R0 ¼ 6C, and R ¼ 4C alkanes, but one also has to include the two carboxyl carbons in the diacid to get the number it designates to the chain. The structures of these diamine monomers are shown in Fig. 8.2, the diacid monomers are shown in Fig. 8.3. Figure 8.4 shows the amino acid monomers. These structures only show the functional groups, the CH2 connecting groups are implied at the bond intersections. All polyamides tend to absorb moisture that can affect their properties. Properties are often reported as dry as molded (DAM) or conditioned [usually at equilibrium in 50% relative humidity (RH) at 23 C]. The absorbed water tends to act like a plasticizer and can have a significant effect on the plastics properties.
Table 8.1 Monomers Used to Make Specific Polyamides/Nylons Polyamide/Nylon Type
Monomers Used to Make
Nylon 6
Caprolactam
Nylon 11
Aminoundecanoic acid
Nylon 12
Aminolauric acid
Nylon 66
1,6-Hexamethylene diamine and adipic acid
Nylon 610
1,6-Hexamethylene diamine and sebacic acid
Nylon 612
1,6-Hexamethylene diamine and 1,12-dodecanedioic acid
Nylon 666
Copolymer based on nylon 6 and nylon 66
Nylon 46
1,4-Diaminobutane and adipic acid
Nylon amorphous
Trimethyl hexamethylene diamine and TPA
PPA
Any diamine and IPA and/or TPA
Figure 8.1 Generalized polyamide reaction.
Permeability Properties of Plastics and Elastomers. DOI: 10.1016/B978-1-4377-3469-0.10008-6 Copyright Ó 2012 Elsevier Inc. All rights reserved.
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Figure 8.2 Chemical structures of diamines used to make polyamides.
Figure 8.3 Chemical structures of diacids used to make polyamides. Figure 8.4 Chemical structures of amino acids used to make polyamides.
8.1 Amorphous Polyamide (Nylon) Amorphous nylon is designed to give no crystallinity to the polymer structure. One such amorphous nylon is shown in Fig. 8.5. The tertiary butyl group attached to the amine molecule is bulky and disrupts this molecule’s ability to crystallize. This particular amorphous nylon is
Figure 8.5 Chemical structure of amorphous nylon.
8: P OLYAMIDES (N YLONS )
123 Blending even low percentages (20%) of SelarÒ PA with nylon 6, nylon 66, and nylon copolymers will result in a product that behaves like an amorphous polymer. These blends retain all of the advantages of the SelarÒ PA resin with some of the mechanical property advantages of semicrystalline nylon. Manufacturers and trade names: DuPontÔ SelarÒ PA, EMS Chemie GrivoryÒ G 16, and GrivoryÒ G21. Applications and uses: Used as a monolayer or as a component of multilayer flexible in meat and cheese packages as well as rigid packaging; multilayer or monolayer are used in transparent hollow vessels (bottles), packaging films, and deep-drawn plates (Tables 8.2e8.7, Figs. 8.6e8.9).
sometimes designated at nylon 6-3-T. Amorphous polymers can have properties that differ significantly from crystalline types, one of which is optical transparency. Some of the amorphous nylon characteristics are as follows: Crystal-clear, high optical transparency High mechanical stability High heat deflection temperature High impact strength Good chemical resistance compared to other plastics Good electrical properties Low mold shrinkage
Table 8.2 Permeation of Oxygen at 23 C through EMS Chemie GrivoryÒ G16 and GrivoryÒ G21 Amorphous Nylon1 Grade
G16
G21
G16
G21
RH (%)
0
0
85
85
ASTM D3985
DIN 53380
ASTM D3985
DIN 53380
0.512
0.4
Test method Source document units, gas permeability (cm3/m2 day bar)
30 1.54
Normalized units, permeability coefficient (cm3 mm/m2 day atm)
1.5
Table 8.3 Water Vapor Permeation at 23 C through EMS Chemie GrivoryÒ G16 and GrivoryÒ G21 Amorphous Nylon (0.05 mm)1 Grade
G16
G21
RH (%)
0
85
ASTM D3985
DIN 53122
Test method Source document units, vapor transmission rate (g/100 in.2 day)
0.9
Source document units, vapor transmission rate (g/m2 day)
7
2
Normalized units, vapor transmission rate (g mm/m day)
0.005
0.35
Table 8.4 Carbon Dioxide and Nitrogen at 23 C through EMS Chemie GrivoryÒ G16 Amorphous Nylon1 Penetrant
Carbon dioxide
RH (%) Test method 3
2
Permeability coefficient (cm mm/m day atm)
Nitrogen
0
85
0
EMS method
EMS method
DIN 53380
4.57
2.05
0.512
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Table 8.5 Permeation of Carbon Dioxide vs. Temperature and Humidity through DuPontÔ SelarÒ PA Amorphous Nylon2 Temperature ( C)
0
30
RH (%)
0e5
95 e100
0e5
95 e100
Source document units, permeability coefficient (cc mil/100 in.2 day atm)
5.5
12.2
18
9.8
Normalized units, permeability coefficient (cm3 mm/m2 day atm)
2.16
4.8
7.07
3.85
Table 8.6 Water Vapor at 90% RH through DuPontÔ SelarÒ PA Amorphous Nylon3 Temperature ( C)
37.8
40
Source document units, vapor transmission rate (g mil/ 100 in.2 day)
1.2
1.4
Normalized units, vapor transmission rate (g mm/m2 day)
0.47
0.55
Table 8.7 Oxygen Permeation of DuPontÔ SelarÒ Blends with Nylon 62 % SelarÒ PA 3426 in Blend Temperature
RH
0
20
30
50
80
100
Source Document Units; Permeability Coefficient (cm3 mil/100 in.2 day atm) 0
0e5
0.9
0.9
0.9
0.9
0.9
0.8
0
95e100
3.7
2.0
1.3
0.5
0.4
0.3
30
0e5
4.0
3.9
3.9
3.9
3.9
3.8
30
95e100
15.0
14.0
12.0
9.1
5.6
1.5
Normalized Units; Permeability Coefficient (cm3 mm/m2 day atm) 0
0e5
0.4
0.4
0.4
0.4
0.4
0.3
0
95e100
1.5
0.8
0.5
0.2
0.2
0.1
30
0e5
1.6
1.5
1.5
1.5
1.5
1.5
30
95e100
5.9
5.5
4.7
3.6
2.2
0.6
See also Figs. 8.6e8.10.
E LASTOMERS
8: P OLYAMIDES (N YLONS )
125
Figure 8.6 Permeation of oxygen vs. temperature at 10% and 95% RH through DuPontÔ SelarÒ amorphous polyamide.2
Figure 8.7 Permeation of carbon dioxide vs. temperature through DuPontÔ SelarÒ PA and nylon 6 at 10% and 95% RH.2
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Figure 8.8 Permeation of carbon dioxide vs. RH through DuPontÔ SelarÒ PA amorphous nylon.3
Figure 8.9 Permeation of oxygen vs. RH through DuPontÔ SelarÒ PA amorphous nylon.4
8.2 Polyamide 6 (Nylon 6) Nylon 6 begins as pure caprolactam, which is a ring-structured molecule. This is unique in that the ring is opened and the molecule polymerizes with itself. Since caprolactam has six carbon atoms, the
nylon that it produces is called nylon 6, which is nearly the same as nylon 66 described in Section 8.5. The structure of nylon 6 is shown in Fig. 8.11 with the repeating unit in the brackets. The CAS Number is 628-02-4.
8: P OLYAMIDES (N YLONS )
127
Figure 8.10 Permeation of oxygen vs. temperature through blends of DuPontÔ SelarÒ with nylon 6.2
Figure 8.11 Chemical structure of nylon 6.
Some of the nylon 6 characteristics are as follows: Outstanding balance of mechanical properties. Outstanding toughness in equilibrium moisture content. Outstanding chemical resistance and oil resistance. Outstanding wear and abrasion resistance. Almost all grades are self-extinguishing. The flame-resistant grades are rated UL 94VO. Outstanding long-term heat resistance (at a longterm continuous maximum temperature ranging between 80 and 150 C). Grades reinforced with glass fiber and other materials offer superior elastic modulus and strength.
Offers low gasoline permeability and outstanding gas barrier properties. Highest rate of water absorption and highest equilibrium water content (8% or more). Excellent surface finish even when reinforced. Poor chemical resistance to strong acids and bases. Manufacturers and trade names: BASF UltramidÒ B, Honeywell CapranÒ and AegisÒ , EMS GrilonÒ B, UBE Industries. Applications and uses: Multilayer packaging, food and medical, industrial containers, and automotive underhood reservoirs (Tables 8.8e8.14, Fig. 8.10).
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Table 8.8 Permeation of Gases at Various Temperatures through Honeywell Plastics CapronÒ Nylon 6 Films5 Permeability Coefficient Normalized Units (cm3 mm/m2 day atm)
Source Document Units (cm3/100 in.2 day atm) Permeant
0 C
23 C
50 C
0 C
23 C
50 C
Oxygen
0.5
2.6
14
0.2
1.02
5.5
Nitrogen
0.2
0.9
12
0.08
0.35
4.7
Carbon dioxide
0.6
4.7
44
0.24
1.8
17.3
Film thickness: 0.0254 mm; RH: 0%. Table 8.9 Water Vapor through Honeywell Plastics CapronÒ Nylon 6 Films6 Temperature ( C)
23
23
37.8
37.8
Film thickness (mm)
0.019
0.0254
0.019
0.0254
Relative Humidity (%)
50
50
90
90
Source document units vapor permeation rate (g/day 100 in.2)
0.08
0.6
24e26
19e20
Normalized units vapor permeation rate WVTR (g mm/m2 day)
0.24
0.24
7.1e7.7
5.6e5.9
Table 8.10 Permeation of Gases at 23 C and 0% RH through Honeywell Plastics AegisÒ Nylon 6 Films6 (Applies to H73QP, H73ZP, H86MP, H85NP, H85QP, H100MP, H100QP, H100ZP, H135KQP, H135MP, H135QP, H135WP, H135ZP, H155MP, H155QP, H155WP, H155ZP, H205QP) Permeability Coefficient Permeate
Source Document Units (cm3 mil/m2 day atm)
Normalized Units (cm3 mil/m2 day atm)
Oxygen
40.3
1.02
Nitrogen
14
0.36
Carbon dioxide
72.8
1.85
Table 8.11 Permeation of Oxygen and Water Vapor through UBE Industries Nylon 67 Oxygen
Water Vapor
Source Document Units (cm3/m2 day)
Normalized Units (g/m2 day)
ASTM D3985
JIS Z-0208
1022B
41
125
1030B
41
125
1022FDX99
41
125
1022C2
25
65
Grade Test method
8: P OLYAMIDES (N YLONS )
129
Table 8.12 Permeation of Oxygen through Oriented and Un-Oriented Nylon 63 Oriented
Temperature C
Unoriented
Source Document Units; Permeability Coefficient (cm3 25 mm/ m2 day atm)
Normalized Units; Permeability Coefficient (cm3 mm/ m2 day atm)
Source Document Units; Permeability Coefficient (cm3 25 mm/ m2 day atm)
Normalized Units; Permeability Coefficient (cm3 mm/ m2 day atm)
7.59
0.19
22.3
0.57
78.7
2
5 23
25.6
0.7
35
51.2
1.3
155
3.9
Table 8.13 Permeation of Oxygen, Carbon Dioxide, and Nitrogen at 23 C through EMS GrivoryÒ GrilonÒ F 34 Type 6 Nylon8 Permeability Coefficient RH (%)
Source Document Units (cm3/m2 day atm)
Normalized Units (cm3 mm/m2 day atm)
0
25
1.26
85
100
5.05
Nitrogen
0
10
0.5
Carbon dioxide
0
65
3.28
Permeant Oxygen
Thickness: 0.05 mm; test methods: DIN 53380, DIN 53122.
Table 8.14 Oxygen, Carbon Dioxide, Nitrogen, and Water Vapor through EMS GrilonÒ F 50 Type 6 Nylon7 Permeability Coefficient RH (%)
Source Document Units (cm3/m2 day atm)
Normalized Units (cm3 mm/m2 day atm)
0
25
1.26
85
70
3.53
Nitrogen
0
10
0.5
Carbon dioxide
0
80
4.04
85
250
Permeant Oxygen
12.6
Thickness: 0.05 mm; test methods: DIN 53380, DIN 53122. See also Figs. 8.12e8.14.
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Figure 8.12 Permeation of carbon dioxide vs. temperature through nylon 6 at 10% RH and 95% RH.
Figure 8.13 Permeation of hydrogen sulfide vs. temperature through DuPontÔ nylon 6.9
8: P OLYAMIDES (N YLONS )
131
Figure 8.13 Continued
Figure 8.14 Chemical structure of nylon 11.
8.3 Polyamide 11 (Nylon 11) Nylon 11 has only one monomer, aminoundecanoic acid. It has the necessary amine group at one end and the acid group at the other. It polymerizes with itself to produce the polyamide containing 11 carbon atoms between the nitrogen of the amide groups. Its structure is shown in Fig. 8.15 and it has a CAS number of 25035-04-5. RilsanÒ PA 11 is produced from a “green” raw materialdcastor beans. Some of the nylon 11 characteristics are as follows: Low water absorption for nylon (2.5% at saturation)
Reasonable UV resistance Higher strength Ability to accept high loading of fillers Better heat resistance than nylon 12 More expensive than nylon 6 or nylon 6/6 Relatively low impact strength Manufacturers and trade names: Arkema RilsanÒ B, Suzhou Hipro Polymers HiprolonÒ . Applications and uses: Automotive: fuel and brake lines, ski boots, tennis racquets, medical catheters, and tubing (Table 8.15, Figs. 8.15 and 8.16).
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Figure 8.15 Permeability vs. temperature of various gases through RilsanÒ BESNO P40TL Nylon 11.11
Table 8.15 Permeation of Various Gases at 20 C through Arkema RilsanÒ PA1110 Permeability Coefficient Permeant Gas
Source Document Units, 109 (cm3 cm/cm2 s bar)
RilsanÒ Grade
BESNO TL
Hydrogen
7
Nitrogen
0.15
Oxygen
2
Carbon dioxide
7
Water
15
BESNO TL 61
131
18 6
61
0.6
53 0.35
30 0.15
BESNO P40TL
1.3
0.04
Hydrogen sulfide Methane
BESNO P40TL
Normalized Units (cm3 mm/m2 day atm)
263 1
5
Ethane
2.3
20
Propane
0.75
7
Butane
5.4
47
See also Figs. 8.16 and 8.17.
8: P OLYAMIDES (N YLONS )
133
Figure 8.16 Permeability vs. temperature of natural gas (composition: 85% methane, 8% propane, and 2% butane) through RilsanÒ BESNO P40TL Nylon 11.11
8.4 Polyamide 12 (Nylon 12) Nylon 12 has only one monomer, aminolauric acid. It has the necessary amine group at one end and the acid group at the other. It polymerizes with itself to produce the polyamide containing 12 carbon atoms between the two nitrogen atoms of the two amide groups. Its structure is shown in Fig. 8.17. The properties of semicrystalline polyamides are determined by the concentration of amide groups in the macromolecules. Polyamide 12 has the lowest amide group concentration of all commercially available polyamides thereby substantially promoting its characteristics: Lowest moisture absorption (~2%): Parts show largest dimensional stability under conditions of changing humidity.
Exceptional impact and notched impact strength, even at temperatures well below the freezing point. Good to excellent resistance against greases, oils, fuels, hydraulic fluids, various solvents, salt solutions, and other chemicals. Exceptional resistance to stress cracking, including metal parts encapsulated by injection molding or embedded. Excellent abrasion resistance. Low coefficient of sliding friction. Noise and vibration damping properties. Good fatigue resistance under high-frequency cyclical loading condition. High processability. Expensive. Lowest strength and heat resistance of any Polyamide unmodified generic.
Figure 8.17 Chemical structure of nylon 12.
Manufacturers and trade names: Arkema RilsanÒ A, EMS-GrivoryÒ GrilamidÒ , ExopackÒ DartekÒ (Tables 8.16 and 8.17, Fig. 8.18).
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Table 8.16 Permeation of UBE 303 XA Nylon 12 Resin7 Permeant Test method Source document units 303XA
Oxygen
Water Vapor
ASTM D3985
JIS Z-0208
2
2
cm /m day
g/m2 day
1050
50
Table 8.17 Permeation of EMS-GrivoryÒ Grilamid L 25 Nylon 12 Resin11
Permeant Water vapor
Conditions
Test Method
23 C, 85% RH
DIS 15106-1/-2
Source Document Units
Normalized Units
(g/m2 day)
(g mm/m2 day)
8 3
Oxygen
23 C, 0% RH
23 C, 85% RH Carbon dioxide
23 C, 0% RH
23 C, 85% RH
2
0.4 3
(cm /m day bar)
(cm mm/ m2 day bar)
DIS 15105-1/-2
350
17.7
DIS 15105-1/-2
370
18.7
DIS 15105-1/-2
1500
76
DIS 15105-1/-2
1600
81
See also Fig. 8.19. Thickness: 0.05 mm.
Figure 8.18 Permeability vs. temperature of natural gas (composition: 85% methane, 8% propane, and 2% butane) through RilsanÒ AESNO P40TL Nylon 12.10
8: P OLYAMIDES (N YLONS )
135
8.5 Polyamide 66 (Nylon 66)
Almost all grades are self-extinguishing. The flame-resistant grades are rated UL 94 V0.
The structure of nylon 66 is shown in Fig. 8.19. The CAS number is 32131-17-2. Some of the nylon 66 characteristics are as follows:
Outstanding long-term heat resistance (at a longterm continuous maximum temperature ranging between 80 and 150 C). Grades reinforced with glass fiber and other materials offer superior elastic modulus and strength.
Outstanding balance of mechanical properties. Outstanding toughness in equilibrium moisture content.
Offers low gasoline permeability and outstanding gas barrier properties.
Outstanding resistance.
High water absorption.
chemical
resistance
and
oil
Outstanding wear and abrasion resistance.
Poor chemical resistance to strong acids and bases.
Figure 8.19 Chemical structure of nylon 66.
Manufacturers and trade names: Exopack Performance Films Inc. DartekÒ , DuPontÔ ZytelÒ . Applications and uses: Packaging meat and cheese, industrial end uses, pouch and primal bag, stiff packages, snacks, condiments, shredded cheese, and coffee. Wrapping fine art, potable water, and electrical applications (Tables 8.18e8.22).
Table 8.18 Permeation of Oxygen and Water Vapor through ExopackÒ Performance Films Inc. DartekÒ Nylon 6,6 Films12
DartekÒ Product
Features
Thickness (mm)
Oxygen Permeability Coefficient (cm3 mm/ m2 day atm)
Water Vapor Transmission Rate (cm3 mm/ m2 day atm)
B-601
PVDF coated one side
0.025
0.19
0.23
B-602
PVDF coated one side
0.038
0.29
0.34
F-101
Cast film
0.025
1.4
7.38
N-201
For pouch and bag
0.025
1.4
7.38
O-401
Oriented in machine direction
0.015
0.59
2.18
SF-502
Super formable
0.076
3.6
UF-412
Oriented with slip properties
0.015
0.59
2.18
Table 8.19 Permeation of Oxygen and Carbon Dioxide through BASF Ultramid A5 Nylon 66 Film Permeability Coefficient Permeant Oxygen Carbon dioxide
RH (%)
Source Document Units (cm3 100 mm/m2 day bar)
Normalized Units (cm3 mm/m2 day atm)
40
6e7
0.61e0.71
0
45
4.6
Test method: DIN53380; thickness: 0.02 mm.
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Table 8.20 Permeation of Water Vapor through BASF Ultramid A5 Nylon 66 Film Film Type
Vapor Transmission Rate Source Document Units (g 100 mm/m day)
Normalized Units (g mm/m2 day)
11e12
1.1e1.2
8
0.8
Flat Film Tubular Film
RH gradient: 85%e0%; standard test method: DIN 53122. Table 8.21 Permeation of Various Gases at 23 C and 50% RH through DuPontÔ Zytel 42 Nylon 66 Film13 Permeant
Permeability Coefficient Source Document Units (cm3 mil/100 in.2 day atm)
Normalized Units (cm3 mm/m2 day atm)
Oxygen
2
0.8
Carbon dioxide
9
3.5
Nitrogen
0.7
0.3
Helium
150
59.1
Table 8.22 Permeation of Liquids through DuPontÔ Zytel 42 Nylon 66 Bottles14 Liquid
Vapor permeation rate (g mm/m2 day)
Kerosene
0.08
Methyl salicylate
0.08
Motor oil (SAE 10)
0.08
Toluene
0.08
Fuel oil B
0.2
Water
1.2e2.4
Carbon tetrachloride
2.0
VMP naphtha
2.4
Thickness: 2.54 mm.
8.6 Polyamide 66/610(Nylon 66/ 610) Nylon 66/610 is a copolymer made from hexamethylenediamine, adipic acid, and sebacic acid. Its structure is represented in Fig. 8.20.
Figure 8.20 Structure of polyamide 66/610.
Manufacturers and trade names: EMS-GrivoryÒ GrilonÒ . Applications and uses: Flexible packaging for foodstuff and medical packaging such as IV bags (Table 8.23).
8: P OLYAMIDES (N YLONS )
137
Table 8.23 Permeation of Oxygen, Carbon Dioxide, Nitrogen, and Water Vapor at 23 C through EMS-GrivoryÒ GrilonÒ BM 20 SBG15 Permeability Coefficient Permeant
Test Method
RH (%)
Source Document Units (cm3/m2 day bar)
Normalized Units (cm3 mm/m2 day atm)
Oxygen
ISO 15105-1
0
25
1.3
Oxygen
ISO 15105-1
85
70
3.5
Carbon dioxide
ISO 15105-2
0
80
4.1
Carbon dioxide
ISO 15105-2
85
250
12.7
DIN 53380
0
15
0.8
Nitrogen
Vapor Transmission Rate
Water vapor
ISO 15106-1
Source Document Units (g/m2 day)
Normalized Units (g mm/m2 day)
20
1
85
Thickness: 0.050 mm.
8.7 Polyamide 6/12 (Nylon 6/12) The structure of nylon 6/12 is given in Fig. 8.21. The CAS number is 24936-74-1. Some of the nylon 6/12 characteristics are as follows: High impact strength Very good resistance to greases, oils, fuels, hydraulic fluids, water, alkalis, and saline
Very good stress cracking resistance, even when subjected to chemical attack and when used to cover metal parts Low coefficients of sliding friction and high abrasion resistance, even when running dry Heat deflection temperature (melting point nearly 40 C higher than Nylon 12) Tensile and flexural strength Outstanding recovery at high wet strength
Figure 8.21 Chemical structure of nylon 6/12.
Manufacturers and trade names: EMSGrivoryÒ dGrilonÒ CF, CR, Ube Industries. Applications: Multilayer food packaging and boil in bag (Tables 8.24e8.29).
Table 8.24 Permeation of Oxygen and Carbon Dioxide at 23 C through EMS-GrivoryÒ GrilonÒ CF 6 Nylon 6/12 Film14 Permeation Coefficient Permeant
Test Method
RH (%)
Source Document Units (cm3/m2 day bar)
Oxygen
ISO 15105-1
0
120
6
ISO 15105-1
85
200
10
ISO 15105-2
0
400
20
ISO 15105-2
85
800
41
Carbon dioxide
Thickness: 0.050 mm.
Normalized Units (cm3 mm/m2 day atm)
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Table 8.25 Permeation of Oxygen and Carbon Dioxide at 23 C through EMS-GrivoryÒ GrilonÒ CA 6 Nylon 6/12 Film14 Permeation Coefficient Permeant
Test Method
RH (%)
Source Document Units (cm3/m2 day bar)
Normalized Units (cm3 mm/m2 day atm)
Oxygen
ISO 15105-1
0
150
8
ISO 15105-1
85
250
13
ISO 15105-2
0
450
23
ISO 15105-2
85
850
43
Carbon dioxide
Thickness: 0.050 mm. Table 8.26 Permeation of Oxygen and Carbon Dioxide at 23 C through EMS-GrivoryÒ GrilonÒ CF 7 Nylon 6/12 Film16 Permeation Coefficient Permeant
Test Method
RH (%)
Source Document Units (cm3/m2 day bar)
Normalized Units (cm3 mm/m2 day atm)
Oxygen
ISO 15105-1
0
110
6
ISO 15105-1
85
130
7
ISO 15105-2
0
400
20
ISO 15105-2
85
800
41
Carbon dioxide
Thickness: 0.050 mm. Table 8.27 Permeation of Oxygen and Carbon Dioxide at 23 C through EMS-GrivoryÒ GrilonÒ CR 8 Nylon 6/12 Film17 Permeation Coefficient Permeant
Test Method
RH (%)
Source Document Units (cm3/m2 day bar)
Oxygen
ISO 15105-1
0
80
4.1
ISO 15105-1
85
90
4.6
ISO 15105-2
0
300
15
ISO 15105-2
85
800
41
Carbon dioxide
Normalized Units (cm3 mm/m2 day atm)
Thickness: 0.050 mm. Table 8.28 Permeation of Oxygen, Carbon Dioxide, and Nitrogen at 23 C through EMS-GrivoryÒ GrilonÒ CR 9 Nylon 6/12 Film18 Permeant
Oxygen
Test Method
RH (%)
Permeation Coefficient Source Document Units (cm3/m2 day bar)
Normalized Units (cm3 mm/m2 day atm)
ISO 15105-1
0
55
2.8
ISO 15105-1
85
75
3.8
Carbon dioxide
ISO 15105-2
0
200
10
ISO 15105-2
85
350
18
Nitrogen
DIN 53380
0
15
Thickness: 0.050 mm.
0.8
8: P OLYAMIDES (N YLONS )
139
Table 8.29 Permeation Water Vapor at 23 C through EMS-GrivoryÒ GrilonÒ Nylon 6/12 Films19e21 Vapor Transmission Rate Source Document Units (g/m2 day)
Normalized Units Rate (g mm/m2 day)
CF 6
15
0.8
CA 6
20
1.0
CF 7
15
0.8
CR 8
15
0.8
CR 9
15
0.8
GrilonÒ Product Code
Thickness: 0.050 mm; RH: 85%.
8.8 Polyamide 666 (Nylon 666 or 6/66) This is the name given to copolyamides made from PA 6 and PA 66 building blocks. A precise structure cannot be drawn.
Manufacturers and trade names: Honeywell AegisÔ, UBE Industries, BASF UltramidÒ (Tables 8.30e8.33).
Table 8.30 Permeation of Oxygen, Nitrogen, and Carbon Dioxide through Honeywell AegisÔ Nylon 6/66 Films19 Permeation Coefficient Source Document Units (cm3 mil/100 in.2 day atm)
Permeant Oxygen
Normalized Units (cm3 mm/m2 day atm)
2.40
Nitrogen
1.0
19.8
Carbon dioxide
8.8
287
113
Table 8.31 Permeation of Oxygen at 23 C and Different RHs through UBE Industries LTD. UBE 5033B Nylon 6/66 Films20 Permeation Coefficient Source Document Units (cm3 25 mm/m2 day atm)
Normalized Units (cm3 mm/m2 day atm)
0
52
1.3
65
55
1.4
100
198
5.0
RH (%)
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Table 8.32 Permeation of Oxygen, Carbon Dioxide, Nitrogen, and Water Vapor at 23 C through BASF UltramidÒ C35 Nylon 6/66 Film21 Permeation Coefficient Test Method
RH (%)
Source Document Units (cm3 100 mm/m2 day bar)
Normalized Units (cm3 mm/m2 day atm)
Oxygen
DIN 53380
40
8e9
0.8e0.9
Carbon dioxide
DIN 53380
0
40e45
4.0e4.6
Permeant
Vapor Transmission Rate
Water vapor
Source Document Units (g 100 mm/m2 day)
Normalized Units (g mm/m2 day)
15e18
1.5e1.8
85%e0% Gradient
Thickness: 0.02e0.1 mm.
Table 8.33 Permeation of Oxygen, Carbon Dioxide, Nitrogen, and Water Vapor at 23 C through Honeywell CapranÒ Nylon 6/66 Films22 Permeation Coefficient Normalized Units (cm3 mm/ m2 day atm)
Permeant
Test Method
RH (%)
Source Document Units (cm3/m2 day)
Oxygen
ASTM D3985
0
37.2
0.94
90
232.5
5.91
113.2
2.88
Carbon dioxide
ASTM D1434
0
Nitrogen
ASTM D1434
0
7.75
0.2
Vapor Transmission Rate Source Document Units (g/m2 day) Water vapor
90
341
Normalized Units (g mm/m2 day) 8.7
Thickness: 0.0254 mm.
8.9 Polyamide 6/69 (Nylon 6/6.9) This resin is specifically suited for applications requiring superior toughness and abrasion resistance. Manufacturers and trade names: Shakespeare Monofilaments and Specialty Polymers IsocorÔ, EMS-GrivoryÒ GrilonÒ .
Applications and uses: Cable jacketing, film extrusions, monofilaments/bristles, impact modifier, electrical connectors, and trimmer line (Tables 8.34 and 8.35).
8: P OLYAMIDES (N YLONS )
141
Table 8.34 Permeation of Oxygen, Carbon Dioxide, Nitrogen, and Water Vapor at 23 C through EMS-GrivoryÒ GrilonÒ BM 13 SBG or GrilonÒ BM 13 SBGX23 Permeation Coefficient Permeant
Test Method
RH (%)
Source Document Units (cm3/m2 day bar)
Normalized Units (cm3 mm/m2 day atm)
Oxygen
ISO 15105-1
0
50
2.5
ISO 15105-1
85
100
5.0 6.5
Carbon dioxide
ISO 15105-2
0
130
ISO 15105-2
85
500
Nitrogen
DIN 53380
0
10
25 0.5 Vapor Transmission Rate
Source Document Units (g/m2 day) Water vapor
ISO 15106-1
85
Normalized Units (g mm/m2 day)
15
0.8
Thickness: 0.050 mm. Table 8.35 Permeation of Oxygen, Carbon Dioxide, and Water Vapor at 23 C through EMS-GrivoryÒ GrilonÒ BM 17 SBG24 Permeation Coefficient Permeant
Test Method
RH (%)
Source Document Units (cm3/m2 day bar)
Normalized Units (cm3 mm/m2 day atm)
Oxygen
ISO 15105-1
0
65
3.3
ISO 15105-1
85
45
2.3
ISO 15105-2
0
200
10.3
ISO 15105-2
85
470
23.5
Carbon dioxide
Vapor Transmission Rate
Water vapor
ISO 15106-1
Source Document Units (g/m2 day)
Normalized Units (g mm/m2 day)
18
0.9
85
Thickness: 0.050 mm.
8.10 Polyarylamide Another partially aromatic high-performance polyamide is polyarylamide (PAA). The primary commercial polymer, PAMXD6, is formed by the reaction of m-xylylenediamine and adipic acid giving the structure shown in Figs. 8.22 and 8.23. It is a semicrystalline polymer. Very high rigidity. High strength. Very low creep.
Figure 8.22 Chemical polyarylamide.
structure
of
PAMXD6
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Figure 8.23 Permeation of oxygen vs. RH at 23 C for Mitsubishi gas chemical nylon-MXD6 PAA films.26 Table 8.36 Permeation of CE 10 Fuel Components at 60 C through Solvay Advanced Polymers IxefÒ PAA25 Permeant
Transmission Rate (g mm/m2 day)
Ethanol
0.83
Toluene
0.003
Isooctane
0.001
See also Fig. 8.24.
Excellent surface finish even for a reinforced product even with high glass fiber content.
Applications and uses: Automotive fuel systems and packaging (Table 8.36).
Ease of processing. Good dimensional stability. Slow rate of water absorption.
8.11 Polyphthalamide/High Performance Polyamide
Graphs of multipoint properties of polyamides as a function of temperature, moisture, and other factors are in the following sections. Because the polyamides do absorb water, and that affects the properties, some of the data are dry or better DAM. Some of the data are for conditioned specimen; they have reached equilibrium water absorption from 50% RH at 23 C. Manufacturers and trade names: Solvay Advanced Polymers IxefÒ , Mitsuibishi Gas Chemical Co. Nylon-MXD6, NanocorÒ ImpermÒ .
As a member of the nylon family, it is a semicrystalline material composed from a diacid and a diamine. However, the diacid portion contains at least 55% terephthalic acid (TPA) or isophthalic acid (IPA). TPA or IPA are aromatic components that serve to raise the melting point, glass transition temperature, and generally improve chemical resistance vs. standard aliphatic nylon polymers. The structure of the polymer depends on the ratio of the diacid ingredients and the diamine used and varies from grade to grade. The polymer usually consists of
8: P OLYAMIDES (N YLONS )
143
Figure 8.24 Permeation of oxygen vs. RH NanocorÒ ImpermÒ 105 nanoclay-filled nylon-MXD6 PAA films.27
mixtures of blocks of two or more different segments, four of which are shown in Fig. 8.25. Some of the polyphthalamide (PPA) characteristics are as follows:
High strength or physical properties over a broad temperature range
Very high heat resistance
High processing temperatures
Good chemical resistance Relatively low moisture absorption
Not inherently flame retardant Requires good drying equipment
Manufacturers and trade Advanced Polymers AmodelÒ .
Figure 8.25 Chemical structures of block used to make PPA.
names:
Solvay
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Table 8.37 Permeation of CE 10 Fuel at 60 C Through Solvay Advanced Polymers AmodelÒ PPA (CE10 ¼ 45% isooctane, 45% toluene, 10% ethanol.) Grade
Transmission Rate (g mm/m2 day)
A-1004
0.03
AT-1002
0.4
(CE10 ¼ 45% isooctane, 45% toluene, 10% ethanol.)
Applications and uses: Automotive fuel systems (Table 8.37).
References 1. Data Sheets, GrivoryÒ G16 and G21. EMS Chemie; 2010. 2. DuPontÔ SelarÒ PA3426 Blends with Nylon 6 e General information; 2005. 3. Gas Barrier Properties of EVAL ResinsdTechnical Bulletin No. 110, supplier technical report. EVAL Company of America. 4. Capran Nylon Films, supplier technical report. Allied Signal Inc. 5. AegisÒ product specifications. Honeywell; 2008e2009. 6. UBE nylon extrusion application; 2005. 7. Data Sheets, Characteristics of GrivoryÒ G16, Characteristics of GrivoryÒ G21. EMS Chemie; July 2000. 8. RilsanÒ PA11: Created from a renewable source. Arkema; 2005. 9. Specifications, campus database. EMS Grivory; 2010. 10. DartekÒ Product Specification Sheets, DuPontÔ Packaging Polymers (Product line sold in 2007). 11. ZytelÒ /MinlonÒ design guide-module II, DuPontÔ engineering polymers, 232409D; 1997. 12. Technical Data Sheet-GrilonÒ BM 20 SBG. EMS-Grivory; 2002. 13. Technical Data Sheet-GrilonÒ CF 6. EMSGrivory; 2007. 14. Technical Data Sheet-GrilonÒ CF 7. EMSGrivory; 2002.
15. Technical Data Sheet-GrilonÒ CR 8. EMSGrivory; 2002. 16. Technical Data Sheet-GrilonÒ CR 9. EMSGrivory; 2002. 17. Specification Sheet, Honeywell AegisÔ HCA73MP Nylon 6/6,6 Extrusion Grade Copolymer. 18. Specification Sheet, UBE 5033B Nylon 6/66 Film. 19. Ultramid nylon resins product line, properties, processing, supplier design guide (B 568/1e/4.91). BASF Corporation; 1991. 20. Capron Nylon Resins for FilmsdOperating Manual, supplier technical report (SFF-08). Allied Signal Inc.; 1992. 21. Technical Data Sheet-GrilonÒ BM 13 SBG. EMS-Grivory; 2002. 22. Technical Data Sheet-GrilonÒ BM 17 SBG. EMS-Grivory; 2002. 23. Solvay advanced polymers unveils newly formulated IxefÒ polyarylamide barrier material for automotive fuel systems. News release. Solvay Advanced Polymers; 2007. 24. SelarÒ PA 3426 Barrier Resin, supplier technical report (E-73974). DuPontÔ Company; 1985. 25. Heilman W, Tammela V, Meyer J, Stannett V, Szwarc M. Permeability of polymer films to hydrogen sulfide gas. Ind Eng Chem 1956;48: 821e4. 26. Mitsubishi gas chemical website. Available from: http://www.gasbarriertechnologies.com/ ds_gasbar.html; 2010. 27. Technical Bulletin NC105-O1E, ImpermÒ Grade 105. NANOCOR, INC.; 2008.
properties of the polymer are determined by the R and R0 groups in the monomers. In nylon 6,6, R0 ¼ 6C, and R ¼ 4C alkanes, but one also has to include the two carboxyl carbons in the diacid to get the number it designates to the chain. The structures of these diamine monomers are shown in Fig. 8.2, the diacid monomers are shown in Fig. 8.3. Figure 8.4 shows the amino acid monomers. These structures only show the functional groups, the CH2 connecting groups are implied at the bond intersections. All polyamides tend to absorb moisture that can affect their properties. Properties are often reported as dry as molded (DAM) or conditioned [usually at equilibrium in 50% relative humidity (RH) at 23 C]. The absorbed water tends to act like a plasticizer and can have a significant effect on the plastics properties.
Table 8.1 Monomers Used to Make Specific Polyamides/Nylons Polyamide/Nylon Type
Monomers Used to Make
Nylon 6
Caprolactam
Nylon 11
Aminoundecanoic acid
Nylon 12
Aminolauric acid
Nylon 66
1,6-Hexamethylene diamine and adipic acid
Nylon 610
1,6-Hexamethylene diamine and sebacic acid
Nylon 612
1,6-Hexamethylene diamine and 1,12-dodecanedioic acid
Nylon 666
Copolymer based on nylon 6 and nylon 66
Nylon 46
1,4-Diaminobutane and adipic acid
Nylon amorphous
Trimethyl hexamethylene diamine and TPA
PPA
Any diamine and IPA and/or TPA
Figure 8.1 Generalized polyamide reaction.
Permeability Properties of Plastics and Elastomers. DOI: 10.1016/B978-1-4377-3469-0.10008-6 Copyright Ó 2012 Elsevier Inc. All rights reserved.
121
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Figure 8.2 Chemical structures of diamines used to make polyamides.
Figure 8.3 Chemical structures of diacids used to make polyamides. Figure 8.4 Chemical structures of amino acids used to make polyamides.
8.1 Amorphous Polyamide (Nylon) Amorphous nylon is designed to give no crystallinity to the polymer structure. One such amorphous nylon is shown in Fig. 8.5. The tertiary butyl group attached to the amine molecule is bulky and disrupts this molecule’s ability to crystallize. This particular amorphous nylon is
Figure 8.5 Chemical structure of amorphous nylon.
8: P OLYAMIDES (N YLONS )
123 Blending even low percentages (20%) of SelarÒ PA with nylon 6, nylon 66, and nylon copolymers will result in a product that behaves like an amorphous polymer. These blends retain all of the advantages of the SelarÒ PA resin with some of the mechanical property advantages of semicrystalline nylon. Manufacturers and trade names: DuPontÔ SelarÒ PA, EMS Chemie GrivoryÒ G 16, and GrivoryÒ G21. Applications and uses: Used as a monolayer or as a component of multilayer flexible in meat and cheese packages as well as rigid packaging; multilayer or monolayer are used in transparent hollow vessels (bottles), packaging films, and deep-drawn plates (Tables 8.2e8.7, Figs. 8.6e8.9).
sometimes designated at nylon 6-3-T. Amorphous polymers can have properties that differ significantly from crystalline types, one of which is optical transparency. Some of the amorphous nylon characteristics are as follows: Crystal-clear, high optical transparency High mechanical stability High heat deflection temperature High impact strength Good chemical resistance compared to other plastics Good electrical properties Low mold shrinkage
Table 8.2 Permeation of Oxygen at 23 C through EMS Chemie GrivoryÒ G16 and GrivoryÒ G21 Amorphous Nylon1 Grade
G16
G21
G16
G21
RH (%)
0
0
85
85
ASTM D3985
DIN 53380
ASTM D3985
DIN 53380
0.512
0.4
Test method Source document units, gas permeability (cm3/m2 day bar)
30 1.54
Normalized units, permeability coefficient (cm3 mm/m2 day atm)
1.5
Table 8.3 Water Vapor Permeation at 23 C through EMS Chemie GrivoryÒ G16 and GrivoryÒ G21 Amorphous Nylon (0.05 mm)1 Grade
G16
G21
RH (%)
0
85
ASTM D3985
DIN 53122
Test method Source document units, vapor transmission rate (g/100 in.2 day)
0.9
Source document units, vapor transmission rate (g/m2 day)
7
2
Normalized units, vapor transmission rate (g mm/m day)
0.005
0.35
Table 8.4 Carbon Dioxide and Nitrogen at 23 C through EMS Chemie GrivoryÒ G16 Amorphous Nylon1 Penetrant
Carbon dioxide
RH (%) Test method 3
2
Permeability coefficient (cm mm/m day atm)
Nitrogen
0
85
0
EMS method
EMS method
DIN 53380
4.57
2.05
0.512
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Table 8.5 Permeation of Carbon Dioxide vs. Temperature and Humidity through DuPontÔ SelarÒ PA Amorphous Nylon2 Temperature ( C)
0
30
RH (%)
0e5
95 e100
0e5
95 e100
Source document units, permeability coefficient (cc mil/100 in.2 day atm)
5.5
12.2
18
9.8
Normalized units, permeability coefficient (cm3 mm/m2 day atm)
2.16
4.8
7.07
3.85
Table 8.6 Water Vapor at 90% RH through DuPontÔ SelarÒ PA Amorphous Nylon3 Temperature ( C)
37.8
40
Source document units, vapor transmission rate (g mil/ 100 in.2 day)
1.2
1.4
Normalized units, vapor transmission rate (g mm/m2 day)
0.47
0.55
Table 8.7 Oxygen Permeation of DuPontÔ SelarÒ Blends with Nylon 62 % SelarÒ PA 3426 in Blend Temperature
RH
0
20
30
50
80
100
Source Document Units; Permeability Coefficient (cm3 mil/100 in.2 day atm) 0
0e5
0.9
0.9
0.9
0.9
0.9
0.8
0
95e100
3.7
2.0
1.3
0.5
0.4
0.3
30
0e5
4.0
3.9
3.9
3.9
3.9
3.8
30
95e100
15.0
14.0
12.0
9.1
5.6
1.5
Normalized Units; Permeability Coefficient (cm3 mm/m2 day atm) 0
0e5
0.4
0.4
0.4
0.4
0.4
0.3
0
95e100
1.5
0.8
0.5
0.2
0.2
0.1
30
0e5
1.6
1.5
1.5
1.5
1.5
1.5
30
95e100
5.9
5.5
4.7
3.6
2.2
0.6
See also Figs. 8.6e8.10.
E LASTOMERS
8: P OLYAMIDES (N YLONS )
125
Figure 8.6 Permeation of oxygen vs. temperature at 10% and 95% RH through DuPontÔ SelarÒ amorphous polyamide.2
Figure 8.7 Permeation of carbon dioxide vs. temperature through DuPontÔ SelarÒ PA and nylon 6 at 10% and 95% RH.2
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Figure 8.8 Permeation of carbon dioxide vs. RH through DuPontÔ SelarÒ PA amorphous nylon.3
Figure 8.9 Permeation of oxygen vs. RH through DuPontÔ SelarÒ PA amorphous nylon.4
8.2 Polyamide 6 (Nylon 6) Nylon 6 begins as pure caprolactam, which is a ring-structured molecule. This is unique in that the ring is opened and the molecule polymerizes with itself. Since caprolactam has six carbon atoms, the
nylon that it produces is called nylon 6, which is nearly the same as nylon 66 described in Section 8.5. The structure of nylon 6 is shown in Fig. 8.11 with the repeating unit in the brackets. The CAS Number is 628-02-4.
8: P OLYAMIDES (N YLONS )
127
Figure 8.10 Permeation of oxygen vs. temperature through blends of DuPontÔ SelarÒ with nylon 6.2
Figure 8.11 Chemical structure of nylon 6.
Some of the nylon 6 characteristics are as follows: Outstanding balance of mechanical properties. Outstanding toughness in equilibrium moisture content. Outstanding chemical resistance and oil resistance. Outstanding wear and abrasion resistance. Almost all grades are self-extinguishing. The flame-resistant grades are rated UL 94VO. Outstanding long-term heat resistance (at a longterm continuous maximum temperature ranging between 80 and 150 C). Grades reinforced with glass fiber and other materials offer superior elastic modulus and strength.
Offers low gasoline permeability and outstanding gas barrier properties. Highest rate of water absorption and highest equilibrium water content (8% or more). Excellent surface finish even when reinforced. Poor chemical resistance to strong acids and bases. Manufacturers and trade names: BASF UltramidÒ B, Honeywell CapranÒ and AegisÒ , EMS GrilonÒ B, UBE Industries. Applications and uses: Multilayer packaging, food and medical, industrial containers, and automotive underhood reservoirs (Tables 8.8e8.14, Fig. 8.10).
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Table 8.8 Permeation of Gases at Various Temperatures through Honeywell Plastics CapronÒ Nylon 6 Films5 Permeability Coefficient Normalized Units (cm3 mm/m2 day atm)
Source Document Units (cm3/100 in.2 day atm) Permeant
0 C
23 C
50 C
0 C
23 C
50 C
Oxygen
0.5
2.6
14
0.2
1.02
5.5
Nitrogen
0.2
0.9
12
0.08
0.35
4.7
Carbon dioxide
0.6
4.7
44
0.24
1.8
17.3
Film thickness: 0.0254 mm; RH: 0%. Table 8.9 Water Vapor through Honeywell Plastics CapronÒ Nylon 6 Films6 Temperature ( C)
23
23
37.8
37.8
Film thickness (mm)
0.019
0.0254
0.019
0.0254
Relative Humidity (%)
50
50
90
90
Source document units vapor permeation rate (g/day 100 in.2)
0.08
0.6
24e26
19e20
Normalized units vapor permeation rate WVTR (g mm/m2 day)
0.24
0.24
7.1e7.7
5.6e5.9
Table 8.10 Permeation of Gases at 23 C and 0% RH through Honeywell Plastics AegisÒ Nylon 6 Films6 (Applies to H73QP, H73ZP, H86MP, H85NP, H85QP, H100MP, H100QP, H100ZP, H135KQP, H135MP, H135QP, H135WP, H135ZP, H155MP, H155QP, H155WP, H155ZP, H205QP) Permeability Coefficient Permeate
Source Document Units (cm3 mil/m2 day atm)
Normalized Units (cm3 mil/m2 day atm)
Oxygen
40.3
1.02
Nitrogen
14
0.36
Carbon dioxide
72.8
1.85
Table 8.11 Permeation of Oxygen and Water Vapor through UBE Industries Nylon 67 Oxygen
Water Vapor
Source Document Units (cm3/m2 day)
Normalized Units (g/m2 day)
ASTM D3985
JIS Z-0208
1022B
41
125
1030B
41
125
1022FDX99
41
125
1022C2
25
65
Grade Test method
8: P OLYAMIDES (N YLONS )
129
Table 8.12 Permeation of Oxygen through Oriented and Un-Oriented Nylon 63 Oriented
Temperature C
Unoriented
Source Document Units; Permeability Coefficient (cm3 25 mm/ m2 day atm)
Normalized Units; Permeability Coefficient (cm3 mm/ m2 day atm)
Source Document Units; Permeability Coefficient (cm3 25 mm/ m2 day atm)
Normalized Units; Permeability Coefficient (cm3 mm/ m2 day atm)
7.59
0.19
22.3
0.57
78.7
2
5 23
25.6
0.7
35
51.2
1.3
155
3.9
Table 8.13 Permeation of Oxygen, Carbon Dioxide, and Nitrogen at 23 C through EMS GrivoryÒ GrilonÒ F 34 Type 6 Nylon8 Permeability Coefficient RH (%)
Source Document Units (cm3/m2 day atm)
Normalized Units (cm3 mm/m2 day atm)
0
25
1.26
85
100
5.05
Nitrogen
0
10
0.5
Carbon dioxide
0
65
3.28
Permeant Oxygen
Thickness: 0.05 mm; test methods: DIN 53380, DIN 53122.
Table 8.14 Oxygen, Carbon Dioxide, Nitrogen, and Water Vapor through EMS GrilonÒ F 50 Type 6 Nylon7 Permeability Coefficient RH (%)
Source Document Units (cm3/m2 day atm)
Normalized Units (cm3 mm/m2 day atm)
0
25
1.26
85
70
3.53
Nitrogen
0
10
0.5
Carbon dioxide
0
80
4.04
85
250
Permeant Oxygen
12.6
Thickness: 0.05 mm; test methods: DIN 53380, DIN 53122. See also Figs. 8.12e8.14.
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Figure 8.12 Permeation of carbon dioxide vs. temperature through nylon 6 at 10% RH and 95% RH.
Figure 8.13 Permeation of hydrogen sulfide vs. temperature through DuPontÔ nylon 6.9
8: P OLYAMIDES (N YLONS )
131
Figure 8.13 Continued
Figure 8.14 Chemical structure of nylon 11.
8.3 Polyamide 11 (Nylon 11) Nylon 11 has only one monomer, aminoundecanoic acid. It has the necessary amine group at one end and the acid group at the other. It polymerizes with itself to produce the polyamide containing 11 carbon atoms between the nitrogen of the amide groups. Its structure is shown in Fig. 8.15 and it has a CAS number of 25035-04-5. RilsanÒ PA 11 is produced from a “green” raw materialdcastor beans. Some of the nylon 11 characteristics are as follows: Low water absorption for nylon (2.5% at saturation)
Reasonable UV resistance Higher strength Ability to accept high loading of fillers Better heat resistance than nylon 12 More expensive than nylon 6 or nylon 6/6 Relatively low impact strength Manufacturers and trade names: Arkema RilsanÒ B, Suzhou Hipro Polymers HiprolonÒ . Applications and uses: Automotive: fuel and brake lines, ski boots, tennis racquets, medical catheters, and tubing (Table 8.15, Figs. 8.15 and 8.16).
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Figure 8.15 Permeability vs. temperature of various gases through RilsanÒ BESNO P40TL Nylon 11.11
Table 8.15 Permeation of Various Gases at 20 C through Arkema RilsanÒ PA1110 Permeability Coefficient Permeant Gas
Source Document Units, 109 (cm3 cm/cm2 s bar)
RilsanÒ Grade
BESNO TL
Hydrogen
7
Nitrogen
0.15
Oxygen
2
Carbon dioxide
7
Water
15
BESNO TL 61
131
18 6
61
0.6
53 0.35
30 0.15
BESNO P40TL
1.3
0.04
Hydrogen sulfide Methane
BESNO P40TL
Normalized Units (cm3 mm/m2 day atm)
263 1
5
Ethane
2.3
20
Propane
0.75
7
Butane
5.4
47
See also Figs. 8.16 and 8.17.
8: P OLYAMIDES (N YLONS )
133
Figure 8.16 Permeability vs. temperature of natural gas (composition: 85% methane, 8% propane, and 2% butane) through RilsanÒ BESNO P40TL Nylon 11.11
8.4 Polyamide 12 (Nylon 12) Nylon 12 has only one monomer, aminolauric acid. It has the necessary amine group at one end and the acid group at the other. It polymerizes with itself to produce the polyamide containing 12 carbon atoms between the two nitrogen atoms of the two amide groups. Its structure is shown in Fig. 8.17. The properties of semicrystalline polyamides are determined by the concentration of amide groups in the macromolecules. Polyamide 12 has the lowest amide group concentration of all commercially available polyamides thereby substantially promoting its characteristics: Lowest moisture absorption (~2%): Parts show largest dimensional stability under conditions of changing humidity.
Exceptional impact and notched impact strength, even at temperatures well below the freezing point. Good to excellent resistance against greases, oils, fuels, hydraulic fluids, various solvents, salt solutions, and other chemicals. Exceptional resistance to stress cracking, including metal parts encapsulated by injection molding or embedded. Excellent abrasion resistance. Low coefficient of sliding friction. Noise and vibration damping properties. Good fatigue resistance under high-frequency cyclical loading condition. High processability. Expensive. Lowest strength and heat resistance of any Polyamide unmodified generic.
Figure 8.17 Chemical structure of nylon 12.
Manufacturers and trade names: Arkema RilsanÒ A, EMS-GrivoryÒ GrilamidÒ , ExopackÒ DartekÒ (Tables 8.16 and 8.17, Fig. 8.18).
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Table 8.16 Permeation of UBE 303 XA Nylon 12 Resin7 Permeant Test method Source document units 303XA
Oxygen
Water Vapor
ASTM D3985
JIS Z-0208
2
2
cm /m day
g/m2 day
1050
50
Table 8.17 Permeation of EMS-GrivoryÒ Grilamid L 25 Nylon 12 Resin11
Permeant Water vapor
Conditions
Test Method
23 C, 85% RH
DIS 15106-1/-2
Source Document Units
Normalized Units
(g/m2 day)
(g mm/m2 day)
8 3
Oxygen
23 C, 0% RH
23 C, 85% RH Carbon dioxide
23 C, 0% RH
23 C, 85% RH
2
0.4 3
(cm /m day bar)
(cm mm/ m2 day bar)
DIS 15105-1/-2
350
17.7
DIS 15105-1/-2
370
18.7
DIS 15105-1/-2
1500
76
DIS 15105-1/-2
1600
81
See also Fig. 8.19. Thickness: 0.05 mm.
Figure 8.18 Permeability vs. temperature of natural gas (composition: 85% methane, 8% propane, and 2% butane) through RilsanÒ AESNO P40TL Nylon 12.10
8: P OLYAMIDES (N YLONS )
135
8.5 Polyamide 66 (Nylon 66)
Almost all grades are self-extinguishing. The flame-resistant grades are rated UL 94 V0.
The structure of nylon 66 is shown in Fig. 8.19. The CAS number is 32131-17-2. Some of the nylon 66 characteristics are as follows:
Outstanding long-term heat resistance (at a longterm continuous maximum temperature ranging between 80 and 150 C). Grades reinforced with glass fiber and other materials offer superior elastic modulus and strength.
Outstanding balance of mechanical properties. Outstanding toughness in equilibrium moisture content.
Offers low gasoline permeability and outstanding gas barrier properties.
Outstanding resistance.
High water absorption.
chemical
resistance
and
oil
Outstanding wear and abrasion resistance.
Poor chemical resistance to strong acids and bases.
Figure 8.19 Chemical structure of nylon 66.
Manufacturers and trade names: Exopack Performance Films Inc. DartekÒ , DuPontÔ ZytelÒ . Applications and uses: Packaging meat and cheese, industrial end uses, pouch and primal bag, stiff packages, snacks, condiments, shredded cheese, and coffee. Wrapping fine art, potable water, and electrical applications (Tables 8.18e8.22).
Table 8.18 Permeation of Oxygen and Water Vapor through ExopackÒ Performance Films Inc. DartekÒ Nylon 6,6 Films12
DartekÒ Product
Features
Thickness (mm)
Oxygen Permeability Coefficient (cm3 mm/ m2 day atm)
Water Vapor Transmission Rate (cm3 mm/ m2 day atm)
B-601
PVDF coated one side
0.025
0.19
0.23
B-602
PVDF coated one side
0.038
0.29
0.34
F-101
Cast film
0.025
1.4
7.38
N-201
For pouch and bag
0.025
1.4
7.38
O-401
Oriented in machine direction
0.015
0.59
2.18
SF-502
Super formable
0.076
3.6
UF-412
Oriented with slip properties
0.015
0.59
2.18
Table 8.19 Permeation of Oxygen and Carbon Dioxide through BASF Ultramid A5 Nylon 66 Film Permeability Coefficient Permeant Oxygen Carbon dioxide
RH (%)
Source Document Units (cm3 100 mm/m2 day bar)
Normalized Units (cm3 mm/m2 day atm)
40
6e7
0.61e0.71
0
45
4.6
Test method: DIN53380; thickness: 0.02 mm.
136
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AND
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Table 8.20 Permeation of Water Vapor through BASF Ultramid A5 Nylon 66 Film Film Type
Vapor Transmission Rate Source Document Units (g 100 mm/m day)
Normalized Units (g mm/m2 day)
11e12
1.1e1.2
8
0.8
Flat Film Tubular Film
RH gradient: 85%e0%; standard test method: DIN 53122. Table 8.21 Permeation of Various Gases at 23 C and 50% RH through DuPontÔ Zytel 42 Nylon 66 Film13 Permeant
Permeability Coefficient Source Document Units (cm3 mil/100 in.2 day atm)
Normalized Units (cm3 mm/m2 day atm)
Oxygen
2
0.8
Carbon dioxide
9
3.5
Nitrogen
0.7
0.3
Helium
150
59.1
Table 8.22 Permeation of Liquids through DuPontÔ Zytel 42 Nylon 66 Bottles14 Liquid
Vapor permeation rate (g mm/m2 day)
Kerosene
0.08
Methyl salicylate
0.08
Motor oil (SAE 10)
0.08
Toluene
0.08
Fuel oil B
0.2
Water
1.2e2.4
Carbon tetrachloride
2.0
VMP naphtha
2.4
Thickness: 2.54 mm.
8.6 Polyamide 66/610(Nylon 66/ 610) Nylon 66/610 is a copolymer made from hexamethylenediamine, adipic acid, and sebacic acid. Its structure is represented in Fig. 8.20.
Figure 8.20 Structure of polyamide 66/610.
Manufacturers and trade names: EMS-GrivoryÒ GrilonÒ . Applications and uses: Flexible packaging for foodstuff and medical packaging such as IV bags (Table 8.23).
8: P OLYAMIDES (N YLONS )
137
Table 8.23 Permeation of Oxygen, Carbon Dioxide, Nitrogen, and Water Vapor at 23 C through EMS-GrivoryÒ GrilonÒ BM 20 SBG15 Permeability Coefficient Permeant
Test Method
RH (%)
Source Document Units (cm3/m2 day bar)
Normalized Units (cm3 mm/m2 day atm)
Oxygen
ISO 15105-1
0
25
1.3
Oxygen
ISO 15105-1
85
70
3.5
Carbon dioxide
ISO 15105-2
0
80
4.1
Carbon dioxide
ISO 15105-2
85
250
12.7
DIN 53380
0
15
0.8
Nitrogen
Vapor Transmission Rate
Water vapor
ISO 15106-1
Source Document Units (g/m2 day)
Normalized Units (g mm/m2 day)
20
1
85
Thickness: 0.050 mm.
8.7 Polyamide 6/12 (Nylon 6/12) The structure of nylon 6/12 is given in Fig. 8.21. The CAS number is 24936-74-1. Some of the nylon 6/12 characteristics are as follows: High impact strength Very good resistance to greases, oils, fuels, hydraulic fluids, water, alkalis, and saline
Very good stress cracking resistance, even when subjected to chemical attack and when used to cover metal parts Low coefficients of sliding friction and high abrasion resistance, even when running dry Heat deflection temperature (melting point nearly 40 C higher than Nylon 12) Tensile and flexural strength Outstanding recovery at high wet strength
Figure 8.21 Chemical structure of nylon 6/12.
Manufacturers and trade names: EMSGrivoryÒ dGrilonÒ CF, CR, Ube Industries. Applications: Multilayer food packaging and boil in bag (Tables 8.24e8.29).
Table 8.24 Permeation of Oxygen and Carbon Dioxide at 23 C through EMS-GrivoryÒ GrilonÒ CF 6 Nylon 6/12 Film14 Permeation Coefficient Permeant
Test Method
RH (%)
Source Document Units (cm3/m2 day bar)
Oxygen
ISO 15105-1
0
120
6
ISO 15105-1
85
200
10
ISO 15105-2
0
400
20
ISO 15105-2
85
800
41
Carbon dioxide
Thickness: 0.050 mm.
Normalized Units (cm3 mm/m2 day atm)
138
P ERMEABILITY P ROPERTIES
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P LASTICS
AND
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Table 8.25 Permeation of Oxygen and Carbon Dioxide at 23 C through EMS-GrivoryÒ GrilonÒ CA 6 Nylon 6/12 Film14 Permeation Coefficient Permeant
Test Method
RH (%)
Source Document Units (cm3/m2 day bar)
Normalized Units (cm3 mm/m2 day atm)
Oxygen
ISO 15105-1
0
150
8
ISO 15105-1
85
250
13
ISO 15105-2
0
450
23
ISO 15105-2
85
850
43
Carbon dioxide
Thickness: 0.050 mm. Table 8.26 Permeation of Oxygen and Carbon Dioxide at 23 C through EMS-GrivoryÒ GrilonÒ CF 7 Nylon 6/12 Film16 Permeation Coefficient Permeant
Test Method
RH (%)
Source Document Units (cm3/m2 day bar)
Normalized Units (cm3 mm/m2 day atm)
Oxygen
ISO 15105-1
0
110
6
ISO 15105-1
85
130
7
ISO 15105-2
0
400
20
ISO 15105-2
85
800
41
Carbon dioxide
Thickness: 0.050 mm. Table 8.27 Permeation of Oxygen and Carbon Dioxide at 23 C through EMS-GrivoryÒ GrilonÒ CR 8 Nylon 6/12 Film17 Permeation Coefficient Permeant
Test Method
RH (%)
Source Document Units (cm3/m2 day bar)
Oxygen
ISO 15105-1
0
80
4.1
ISO 15105-1
85
90
4.6
ISO 15105-2
0
300
15
ISO 15105-2
85
800
41
Carbon dioxide
Normalized Units (cm3 mm/m2 day atm)
Thickness: 0.050 mm. Table 8.28 Permeation of Oxygen, Carbon Dioxide, and Nitrogen at 23 C through EMS-GrivoryÒ GrilonÒ CR 9 Nylon 6/12 Film18 Permeant
Oxygen
Test Method
RH (%)
Permeation Coefficient Source Document Units (cm3/m2 day bar)
Normalized Units (cm3 mm/m2 day atm)
ISO 15105-1
0
55
2.8
ISO 15105-1
85
75
3.8
Carbon dioxide
ISO 15105-2
0
200
10
ISO 15105-2
85
350
18
Nitrogen
DIN 53380
0
15
Thickness: 0.050 mm.
0.8
8: P OLYAMIDES (N YLONS )
139
Table 8.29 Permeation Water Vapor at 23 C through EMS-GrivoryÒ GrilonÒ Nylon 6/12 Films19e21 Vapor Transmission Rate Source Document Units (g/m2 day)
Normalized Units Rate (g mm/m2 day)
CF 6
15
0.8
CA 6
20
1.0
CF 7
15
0.8
CR 8
15
0.8
CR 9
15
0.8
GrilonÒ Product Code
Thickness: 0.050 mm; RH: 85%.
8.8 Polyamide 666 (Nylon 666 or 6/66) This is the name given to copolyamides made from PA 6 and PA 66 building blocks. A precise structure cannot be drawn.
Manufacturers and trade names: Honeywell AegisÔ, UBE Industries, BASF UltramidÒ (Tables 8.30e8.33).
Table 8.30 Permeation of Oxygen, Nitrogen, and Carbon Dioxide through Honeywell AegisÔ Nylon 6/66 Films19 Permeation Coefficient Source Document Units (cm3 mil/100 in.2 day atm)
Permeant Oxygen
Normalized Units (cm3 mm/m2 day atm)
2.40
Nitrogen
1.0
19.8
Carbon dioxide
8.8
287
113
Table 8.31 Permeation of Oxygen at 23 C and Different RHs through UBE Industries LTD. UBE 5033B Nylon 6/66 Films20 Permeation Coefficient Source Document Units (cm3 25 mm/m2 day atm)
Normalized Units (cm3 mm/m2 day atm)
0
52
1.3
65
55
1.4
100
198
5.0
RH (%)
140
P ERMEABILITY P ROPERTIES
OF
P LASTICS
AND
E LASTOMERS
Table 8.32 Permeation of Oxygen, Carbon Dioxide, Nitrogen, and Water Vapor at 23 C through BASF UltramidÒ C35 Nylon 6/66 Film21 Permeation Coefficient Test Method
RH (%)
Source Document Units (cm3 100 mm/m2 day bar)
Normalized Units (cm3 mm/m2 day atm)
Oxygen
DIN 53380
40
8e9
0.8e0.9
Carbon dioxide
DIN 53380
0
40e45
4.0e4.6
Permeant
Vapor Transmission Rate
Water vapor
Source Document Units (g 100 mm/m2 day)
Normalized Units (g mm/m2 day)
15e18
1.5e1.8
85%e0% Gradient
Thickness: 0.02e0.1 mm.
Table 8.33 Permeation of Oxygen, Carbon Dioxide, Nitrogen, and Water Vapor at 23 C through Honeywell CapranÒ Nylon 6/66 Films22 Permeation Coefficient Normalized Units (cm3 mm/ m2 day atm)
Permeant
Test Method
RH (%)
Source Document Units (cm3/m2 day)
Oxygen
ASTM D3985
0
37.2
0.94
90
232.5
5.91
113.2
2.88
Carbon dioxide
ASTM D1434
0
Nitrogen
ASTM D1434
0
7.75
0.2
Vapor Transmission Rate Source Document Units (g/m2 day) Water vapor
90
341
Normalized Units (g mm/m2 day) 8.7
Thickness: 0.0254 mm.
8.9 Polyamide 6/69 (Nylon 6/6.9) This resin is specifically suited for applications requiring superior toughness and abrasion resistance. Manufacturers and trade names: Shakespeare Monofilaments and Specialty Polymers IsocorÔ, EMS-GrivoryÒ GrilonÒ .
Applications and uses: Cable jacketing, film extrusions, monofilaments/bristles, impact modifier, electrical connectors, and trimmer line (Tables 8.34 and 8.35).
8: P OLYAMIDES (N YLONS )
141
Table 8.34 Permeation of Oxygen, Carbon Dioxide, Nitrogen, and Water Vapor at 23 C through EMS-GrivoryÒ GrilonÒ BM 13 SBG or GrilonÒ BM 13 SBGX23 Permeation Coefficient Permeant
Test Method
RH (%)
Source Document Units (cm3/m2 day bar)
Normalized Units (cm3 mm/m2 day atm)
Oxygen
ISO 15105-1
0
50
2.5
ISO 15105-1
85
100
5.0 6.5
Carbon dioxide
ISO 15105-2
0
130
ISO 15105-2
85
500
Nitrogen
DIN 53380
0
10
25 0.5 Vapor Transmission Rate
Source Document Units (g/m2 day) Water vapor
ISO 15106-1
85
Normalized Units (g mm/m2 day)
15
0.8
Thickness: 0.050 mm. Table 8.35 Permeation of Oxygen, Carbon Dioxide, and Water Vapor at 23 C through EMS-GrivoryÒ GrilonÒ BM 17 SBG24 Permeation Coefficient Permeant
Test Method
RH (%)
Source Document Units (cm3/m2 day bar)
Normalized Units (cm3 mm/m2 day atm)
Oxygen
ISO 15105-1
0
65
3.3
ISO 15105-1
85
45
2.3
ISO 15105-2
0
200
10.3
ISO 15105-2
85
470
23.5
Carbon dioxide
Vapor Transmission Rate
Water vapor
ISO 15106-1
Source Document Units (g/m2 day)
Normalized Units (g mm/m2 day)
18
0.9
85
Thickness: 0.050 mm.
8.10 Polyarylamide Another partially aromatic high-performance polyamide is polyarylamide (PAA). The primary commercial polymer, PAMXD6, is formed by the reaction of m-xylylenediamine and adipic acid giving the structure shown in Figs. 8.22 and 8.23. It is a semicrystalline polymer. Very high rigidity. High strength. Very low creep.
Figure 8.22 Chemical polyarylamide.
structure
of
PAMXD6
142
P ERMEABILITY P ROPERTIES
OF
P LASTICS
AND
E LASTOMERS
Figure 8.23 Permeation of oxygen vs. RH at 23 C for Mitsubishi gas chemical nylon-MXD6 PAA films.26 Table 8.36 Permeation of CE 10 Fuel Components at 60 C through Solvay Advanced Polymers IxefÒ PAA25 Permeant
Transmission Rate (g mm/m2 day)
Ethanol
0.83
Toluene
0.003
Isooctane
0.001
See also Fig. 8.24.
Excellent surface finish even for a reinforced product even with high glass fiber content.
Applications and uses: Automotive fuel systems and packaging (Table 8.36).
Ease of processing. Good dimensional stability. Slow rate of water absorption.
8.11 Polyphthalamide/High Performance Polyamide
Graphs of multipoint properties of polyamides as a function of temperature, moisture, and other factors are in the following sections. Because the polyamides do absorb water, and that affects the properties, some of the data are dry or better DAM. Some of the data are for conditioned specimen; they have reached equilibrium water absorption from 50% RH at 23 C. Manufacturers and trade names: Solvay Advanced Polymers IxefÒ , Mitsuibishi Gas Chemical Co. Nylon-MXD6, NanocorÒ ImpermÒ .
As a member of the nylon family, it is a semicrystalline material composed from a diacid and a diamine. However, the diacid portion contains at least 55% terephthalic acid (TPA) or isophthalic acid (IPA). TPA or IPA are aromatic components that serve to raise the melting point, glass transition temperature, and generally improve chemical resistance vs. standard aliphatic nylon polymers. The structure of the polymer depends on the ratio of the diacid ingredients and the diamine used and varies from grade to grade. The polymer usually consists of
8: P OLYAMIDES (N YLONS )
143
Figure 8.24 Permeation of oxygen vs. RH NanocorÒ ImpermÒ 105 nanoclay-filled nylon-MXD6 PAA films.27
mixtures of blocks of two or more different segments, four of which are shown in Fig. 8.25. Some of the polyphthalamide (PPA) characteristics are as follows:
High strength or physical properties over a broad temperature range
Very high heat resistance
High processing temperatures
Good chemical resistance Relatively low moisture absorption
Not inherently flame retardant Requires good drying equipment
Manufacturers and trade Advanced Polymers AmodelÒ .
Figure 8.25 Chemical structures of block used to make PPA.
names:
Solvay
144
P ERMEABILITY P ROPERTIES
OF
P LASTICS
AND
E LASTOMERS
Table 8.37 Permeation of CE 10 Fuel at 60 C Through Solvay Advanced Polymers AmodelÒ PPA (CE10 ¼ 45% isooctane, 45% toluene, 10% ethanol.) Grade
Transmission Rate (g mm/m2 day)
A-1004
0.03
AT-1002
0.4
(CE10 ¼ 45% isooctane, 45% toluene, 10% ethanol.)
Applications and uses: Automotive fuel systems (Table 8.37).
References 1. Data Sheets, GrivoryÒ G16 and G21. EMS Chemie; 2010. 2. DuPontÔ SelarÒ PA3426 Blends with Nylon 6 e General information; 2005. 3. Gas Barrier Properties of EVAL ResinsdTechnical Bulletin No. 110, supplier technical report. EVAL Company of America. 4. Capran Nylon Films, supplier technical report. Allied Signal Inc. 5. AegisÒ product specifications. Honeywell; 2008e2009. 6. UBE nylon extrusion application; 2005. 7. Data Sheets, Characteristics of GrivoryÒ G16, Characteristics of GrivoryÒ G21. EMS Chemie; July 2000. 8. RilsanÒ PA11: Created from a renewable source. Arkema; 2005. 9. Specifications, campus database. EMS Grivory; 2010. 10. DartekÒ Product Specification Sheets, DuPontÔ Packaging Polymers (Product line sold in 2007). 11. ZytelÒ /MinlonÒ design guide-module II, DuPontÔ engineering polymers, 232409D; 1997. 12. Technical Data Sheet-GrilonÒ BM 20 SBG. EMS-Grivory; 2002. 13. Technical Data Sheet-GrilonÒ CF 6. EMSGrivory; 2007. 14. Technical Data Sheet-GrilonÒ CF 7. EMSGrivory; 2002.
15. Technical Data Sheet-GrilonÒ CR 8. EMSGrivory; 2002. 16. Technical Data Sheet-GrilonÒ CR 9. EMSGrivory; 2002. 17. Specification Sheet, Honeywell AegisÔ HCA73MP Nylon 6/6,6 Extrusion Grade Copolymer. 18. Specification Sheet, UBE 5033B Nylon 6/66 Film. 19. Ultramid nylon resins product line, properties, processing, supplier design guide (B 568/1e/4.91). BASF Corporation; 1991. 20. Capron Nylon Resins for FilmsdOperating Manual, supplier technical report (SFF-08). Allied Signal Inc.; 1992. 21. Technical Data Sheet-GrilonÒ BM 13 SBG. EMS-Grivory; 2002. 22. Technical Data Sheet-GrilonÒ BM 17 SBG. EMS-Grivory; 2002. 23. Solvay advanced polymers unveils newly formulated IxefÒ polyarylamide barrier material for automotive fuel systems. News release. Solvay Advanced Polymers; 2007. 24. SelarÒ PA 3426 Barrier Resin, supplier technical report (E-73974). DuPontÔ Company; 1985. 25. Heilman W, Tammela V, Meyer J, Stannett V, Szwarc M. Permeability of polymer films to hydrogen sulfide gas. Ind Eng Chem 1956;48: 821e4. 26. Mitsubishi gas chemical website. Available from: http://www.gasbarriertechnologies.com/ ds_gasbar.html; 2010. 27. Technical Bulletin NC105-O1E, ImpermÒ Grade 105. NANOCOR, INC.; 2008.