polyvinyl fluoride || properties of commercial polyvinyl fluoride films

7 Properties of Commercial PolyvinylFluoride Films

O U T L I N E

7.1 Introduction 151

7.2 Polymer Properties 152

7.3 Characteristics of Commercial PVF Films 157

7.4 Chemical Properties 160

7.5 Optical Properties 160

7.6 Thermal Properties 171

7.7 Electrical Properties 173

7.8 Weathering Performance 180

7.9 Description of Available Product and Properties of

Unoriented PVF Films 185

7.10 Effect of Radiation 189

7.11 NMR Spectrum of Polyvinyl Fluoride 191

References 191

7.1 Introduction

Polyvinyl fluoride (PVF) possesses unique properties such as: excellent

resistance to weathering; outstanding mechanical properties and inertness

toward a wide variety of chemicals, solvents, and staining agents. The fluo-

rine atoms in PVF are largely responsible for its properties of excellent

weatherability, chemical resistance, and mechanical properties. The main

application of PVF is as films that usually contain no plasticizers; thus, they

have good aging properties and remain tough and flexible over a broad tem-

perature range. This chapter presents the key properties of PVF films.

151Ebnesajjad: Polyvinyl Fluoride. DOI: http://dx.doi.org/10.1016/B978-1-4557-7885-0.00007-7

© 2013 Elsevier Inc. All rights reserved.

http://dx.doi.org/10.1016/B978-1-4557-7885-0.00007-7

7.2 Polymer Properties

The physical, chemical, and electrical properties of a polyvinyl fluoride

[24981-14-4] film are shown in Table 7.1.

PVF is a semicrystalline polymer with a planar zigzag chain configura-

tion [2]. It tends to crystallize to a greater extent than polyvinyl chloride.

The degree of crystallinity depends on the polymerization method and the

thermal history of the polymer; reported values range from 20% to 60%

[3]. The significant variation of the degree of crystallinity is thought to be

primarily a function of defect structures. Wide-line NMR and X-ray diffrac-

tion studies show the unit cell to contain two monomer units and have the

dimensions a5 0.857 nm, b5 0.495 nm, and c5 0.252 nm [4]. Similarity to

the phase I crystal form of poly(vinylidene fluoride) suggests an orthorhom-

bic crystal [5].

The relationship of the polymer structure to the melting point and degree

of crystallinity has been the subject of a number of studies. Head-to-head

regio irregularities in PVF are known [3,6,7], and the concentration of such

units has been suggested as the source of variations in the melting point

[8�10]. Commercial PVF contains approximately 12% head-to-head linkages

by 19F nmr and displays a peak melting point of about 190�C [9,11�13].

Both NMR and IR studies have shown PVF to be atactic [3,6,7,9,14,17] and,

as such, variations in stereoregularity are not thought to be a contributor to

variations in melting point.

PVF with controlled amounts of head-to-head units varying from 0% to

30% have been prepared [9,11] by using a chlorine substituent to direct the

course of polymerization of chlorofluoroethylenes and then reductively

dechlorinating the products with tributyltin hydride. This series of polymers

shows melting point distributions ranging from about 220�C for purely head-

to-tail polymer down to about 160�C for polymer containing 30% head-to-

head linkages. This study, however, does not report the extent of branching

in these polymers. Further work has shown that the extent of branching has a

pronounced effect on the melting temperature [12,13]. A change of the poly-

merization temperature from 40�C to 90�C produces a change in branch fre-

quency from 0.3 to 1.35 while the frequency of monomer reversals is nearly

constant (12.56 1%). The peak melting point for this series varies from

186�C (polymerization at 90�C) to 206�C (polymerization at 40�C).

7.2.1 Conformations and Transitions ofPolyvinyl Fluoride

Commercial PVF is atactic and contains approximately 12% head-to-head

linkages [9,11,18,19]. These studies have focused on the relationship between

152 POLYVINYL FLUORIDE

Table 7.1 General Properties of Polyvinyl Fluoride Films [1]

Property Typical Value Test Method Test Condition

PHYSICAL Bursting Strength 29�65 psi Mullen, ASTM D-774-67 22�C (72�F)

Coefficient ofFriction (Film/Metal)

0.18�0.21 ASTM D-1894-78 22�C (72�F)

Density 1.37�1.72 g/cc ASTM D-1505-68 22�C (72�F)

Impact Strength 10�20 in lb/mil Spencer ASTM D-3420-80 22�C (72�F)

Moisture Absorption ,0.5% for most types Water immersion 22�C (72�F)

Water VaporTransmission

9�57 g/m2d ASTM E-96-E-80 39.5�C. 80% RH

Refractive Index 1.40 nD ASTM D-542-50 AbbeRefractometer

30�C (86�F)

Tear Strength

Propagated 15�60 g/mil Elmendorf-ASTM D-1922-67 22�C (72�F)

Initial (Graves) 260�500 g/mil ASTM D-1004-66 22�C (72�F)

Tensile Modulus 300�3803103 psi ASTM D-882-80. Method A100% elong./min�Instron

22�C (72�F)

Ultimate TensileStrength

8�163103 psi ASTM D-882-80. Method A100% elong./min�Instron

22�C (72�F)

Ultimate Elongation 90�250% ASTM D-882-80. Method A100% elong./min�Instron

22�C (72�F)

Ultimate Yield 6000�4900 psi ASTM D-882-80. Method A100% elong./min�Instron

22�C (72�F)

(Continued )

Table 7.1 (Continued)


CHEMICAL ChemicalResistance

No visible effect 1 yr immersion in

Acids 25�C (77�F)

Bases 25�C (77�F)

Solvents 25�C (77�F)

2 hr immersion in

Acids Boiling

Bases Boiling

Solvents Boiling

Strength and appearance notaffected

Soil Burial—5 yr —

Gas Permeability

Carbon Dioxide 11.1 cc/(100 in2)(24 hr)(atm)(mil)

ASTM D-1434-75 24�C (75�F)

Helium 150 cc/(100 in2)(24 hr)(atm)(mil)

ASTM D-1434-75 24�C (75�F)

Hydrogen 58.1 cc/(100 in2)(24 hr)(atm)(mil)

ASTM D-1434-75 24�C (75�F)

Nitrogen 0.25 cc/(100 in2)(24 hr)(atm)(mil)

ASTM D-1434-75 24�C (75�F)

Oxygen 3.2 cc/(100 in2)(24 hr)(atm)(mil)

ASTM D-3985-80 24�C (75�F)

Vapor Permeability(at part. press. orvapor at giventemp.)

Acetic Acid 45 g/(100 m2)(hr)(mil) ASTM E-96-80, modified 24�C (75�F)

Acetone 10,000 g/(100 m2)(hr)(mil) ASTM E-96-80, modified 24�C (75�F)

Benzene 90 g/(100 m2)(hr)(mil) ASTM E-96-80, modified 24�C (75�F)

CarbonTetrachloride

50 g/(100 m2)(hr)(mil) ASTM E-96-80, modified 24�C (75�F)

Ethyl Acetate 1000 g/(100 m2)(hr)(mil) ASTM E-96-80, modified 24�C (75�F)

Ethyl Alcohol 35 g/(100 m2)(hr)(mil) ASTM E-96-80, modified 24�C (75�F)

Hexane 55 g/(100 m2)(hr)(mil) ASTM E-96-80, modified 24�C (75�F)

Weatherability Excellent Florida exposure Facing South at 45� tohorizontal

THERMAL Aging 3000 hr Circulating Air Oven 150�C (302�F)

Heat Sealability Some varieties—see BulletinTD-14

Linear Coefficient ofExpansion

2.831025 in/in/�F

Shrinkage(Type 2) MD and TD

4% at 130�C (266�F) Air Oven, 30 min

(Type 3) TD only 4% at 170�C (338�F) Air Oven, 30 min

(Type 4) TD only 2.5% at 170�C (338�F) Air Oven, 30 min

Temperature Range

Continuous Use 272 to 107�C (2 98 to225�F)

Short Cycles orRelease (1-2 hr)

up to 175�C (350�F)

Zero Strength 260 to 300�C (500 to 570�F) Hot Bar

(Continued )



ELECTRICAL TTR20SG4 TWH20BS3

Corona Endurance(hr)

2.5 6.2 ASTM Suggested T method 60 cPs, 1000 V/mil

Dielectric Constant 8.5 11.0 ASTM D-150-81 1 Kc at 22�C (72�F)

Dielectric Strength(kV/mil)

3.4 3.5 ASTM D-150-81 60 cPs, kV/mil

Dissipation Factor(%)

1.6 1.4 ASTM D-150-81 1000 cPs, 22�C (72�F)

2.7 1.7 ASTM D-150-81 1000 cPs, 70�C (158�F)

4.2 3.4 ASTM D-150-81 10 Kc, 22�C (72�F)

2.1 1.6 ASTM D-150-81 10 Kc, 70�C (158�F)

Volume Resistivity(ohm.cm)

431013 73 1014 ASTM D-257-78 22�C (72�F)

231010 1.531011 ASTM D-257-78 100�C (212�F)

the concentration of head-to-head irregularity and branching on the PVF’s

melting point. Polymer consisting of pure head-to-tail linkages had a melting

point of 220�C as opposed to 160�C for PVF containing 30% head-to-head

reversals [9,11]. Further work has suggested that branching is the key variable

affecting the melting point [18,19]. Melting point varied from 186�C to

206�C when the polymerization temperature was decreased from 90�C to

40�C. This range produced 1.35% to 0.3% branching while monomer reversal

remained constant at about 12.5% [20].

Polyvinyl fluoride has a number of transitions below the melting tempera-

ture, the values of which depend on the measurement techniques. The lower

glass transition occurs at �15�C to �20�C and is believed to relate to relaxa-

tion free from restraint by crystallites. The upper glass transition ranges from

40�C�50�C, apparently due to amorphous regions under restraint by crystal-

lites [13]. Yet another transition occurs at �80�C because of short-chain

amorphous relaxation and another at 150�C associated with premelting intra-

crystalline relaxation.

PVF is nearly insoluble in all solvents below about 100�C % [10,20]. PVF

with more solubility has been produced by modifying the polymer with 0.1%

2-propanol. These resins were characterized in N,N-dimethylformamide solu-

tion containing 0.1 N LiBr. Number average molecular weight (Mn) ranged

from 76,000 to 234,000 as measured by osmometry.

7.3 Characteristics of Commercial PVF Films

PVF films are available in clear or pigmented forms at various degrees of

orientations, surface gloss, and adhesion treatment. Tedlars products are des-

ignated by a code such as TABNMJFP, which should be read according to

the description provided here.

Product Code TABNMJFP for Oriented Tedlars:

T5Tedlars

AB5Describes the film; for example, TR means a transparent film,

whereas WH indicates a white film.

NM5 Film thickness (gauge), ranges from 05�40; for example, 10 refers

to 0.001 inch equivalent to 25 μm, and 15 refers to 0.0015 inch equivalent

to 37 μm.

J5 Surface treatment for adhesion, A5 one-side treated, B5 two-side

treated, and S5 untreated.

1577: PROPERTIES OF COMMERCIAL POLYVINYL FLUORIDE FILMS

F5 Surface gloss, G5 glossy, M5medium gloss, L5 low gloss, and S5satin. E means enhance film for aircraft.

P5Measure of orientation, ranges from 1 to 5; 15most oriented,

55 least oriented, and 35medium orientation. Tedlars is referred to as

Type 3 or Type 5.

Some of the colors of Tedlars produced over the years are as follows:

BB5 bayberry; BK5 black; BR5 brownstone red; CC5 charcoal;

CD5 concord cream; CM5 island ivory; CN5Mediterranean olive; CR5colonial red; CW5 cloud white; DD5 desert sand; DS5 doeskin;

EB5 cameo white; ES5 eggshell; FM5 flame modified; GH5 dawn gray;

GO5Georgian sand; GY5 granite gray; HB5 sable brown; LG5 spruce

green; LY5 sun yellow; MB5misty beige; MR5 low gloss release;

PD5 pepper dust; RB5 royal blue; SB5 Salem blue; SE5 transparent;

TU5 tawny; WB5 antique white; WH5 shell white; WS5warm sand.

Product Code TABNMJHP for Unoriented Tedlars SP:

T5Tedlars

AB5Describes the film; for example, TR means a transparent film,

whereas WH indicates a white film.

NM5 Film thickness (gauge), ranges from 05�20; for example, 10 refers

to 0.001 inch equivalent to 25 μm, and 15 refers to 0.0015 inch equivalent

to 37 μm.

J5 Surface treatment for adhesion, A5 one-side treated, and

S5 untreated.

H5 Surface gloss, H5 high gloss, G5 glossy M5medium gloss,

L5 low gloss, and S5 satin.

P5Carrier or no carrier, can be either 8 or 9; 85with carrier film and

95without carrier film.

Tedlars SP is coated on a carrier film, which is removed before shipping.

It protects the PVF film during surface treatment for adhesion, slitting, and

other handling steps.

An increase in the type number of Tedlars, such as Type 2, Type 3, and

Type 4, indicates lower degree of orientation. Orientation of extrusion cast

films ranges from a high tensile strength, high flex variety (Type 2) to a high

elongation, high tear modification (Type 4), and to minimally oriented Types

5 and unoriented Types 8 and 9 (Tedlars SP).


Type 5 PVF film has minimal orientation, rendering it suitable for applica-

tions in which deep draw and texturing are required. The characteristics of

cleanability, durability, color stability, and color reproducibility are lasting in

this type of film. It is also printable and can be laminated to a variety of sub-

strates. Applications of Type 5 film include formed parts requiring surface

protection such as aircraft cabin interior surfaces containing complex curves.

Because of high degree of formability, this film has ultimate elongation

almost twice that of standard Type 3 film.

Type 9, or Tedlars SP (made by DuPont-proprietary SP technology), is pro-

duced through a web coating technique to minimize orientation. These films are

designed to provide maximum conformability to substrates where deep draw is

required. Figure 7.1 shows an example of a decorative laminate made with PVF

film for an aircraft window section requiring deep draw. When Tedlars SP

films are subjected to high levels of forming, significant recovery stresses do

not develop thanks to the minimal orientation of these films.

Commercial PVF films come with different surface characteristics. Surface

“A” (one side adherable) and “B” (two sides adherable) surfaces are used with

adhesives for bonding to a wide variety of substrates. These surfaces have

excellent compatibility with many classes of adhesives, including acrylics,

polyesters, epoxies, rubbers, and pressure-sensitive mastics. The “S” surface

has excellent antistick properties for use as a mold release agent for epoxies,

Figure 7.1 An aircraft window section requiring deep draw. (Courtesy of

Schneller Corp., www.schneller.com.)


http://www.schneller.com

phenolics, rubbers, and other plastic resins. It is especially suited as a release

sheet for printed circuit board lamination. Outdoor weathering tests on oriented

PVF films have been run since 1970’s. Weather resistance, inertness, and

strength characteristics have allowed its broad use as a finish for metals, hard-

boards, felts, or plastics in architectural, decorative, or industrial uses.

Properties of interest to the electrical industry include excellent hydrolytic

stability and high dielectric strength and dielectric constant. Tedlars PVF

(by DuPont) film is generally available in thicknesses from 0.5 to 2.0 mil,

although at times specialty grades with higher thickness have been produced.

PVF films are strong, flexible, and fatigue-resistant. The resistance to failure

by flexing is outstanding. And the films perform well in temperatures ranging

from approximately �72�C to 107�C (�98�F to 225�F), with intermittent

short-term peaking up to 204�C (400�F). Some physical and thermal proper-

ties of different grades of oriented and nonoriented PVF films are summa-

rized in Tables 7.2 and 7.3, respectively.

7.4 Chemical Properties

PVF film has excellent resistance to chemicals, solvents, and stains. It

retains its film form and strength, even when boiled in strong acids and

bases. At ordinary temperatures, the film is not affected by many classes of

common solvents, including hydrocarbons and chlorinated solvents. It is

impermeable to greases and oils. It is partially soluble in a few highly polar

solvents at temperatures above 149�C (300�F) [23].Table 7.4 gives the chemical resistance of polyvinyl fluoride to a number

of common organic and inorganic chemicals. PVF samples were immersed in

these chemicals at room temperature and at 75�C. No changes were observed

in the PVF samples at the end of the indicated exposure period. Some of

these compounds are quite aggressive toward most plastics. Examples

include: acetone, methyl ethyl ketone, trichloroethylene, phenol, nitric acid,

sulfuric acid, and sodium hydroxide. Table 7.5 shows the stain resistance of

PVF films to a few common and potent agents such as iodine.

PVF films have excellent hydrolytic stability as demonstrated by retention

of flex life, impact strength, and break elongation after 1500 hours of expo-

sure to steam at 100�C.

7.5 Optical Properties

The optical properties of polyvinyl fluoride films have spurred its use in a

variety of outdoor applications such as cladding for siding and trims on


Table 7.2 Typical Properties of Oriented Grades of Tedlars PVF Films [21]

Description

1.0 mil UV Screening

Transparent Type 3

1.0 mil

Transparent

Type 3

1.5 mil Low

Gloss White

Type 3

2.0 mil Satin

White Type 3

Designation Units TUT10BG3 TTR10BG3 TWH15BL3 TWH20BS3 Test Method

Physical Properties

Area Factor ft2/lb 14.0 14.0 87 60

m2/kg 28.7 28.7 17.8 12.3

Ultimate Tensile kpsi 13 13 8 9 Instron ASTM D-882-80

Strength, Min.

(MD)

MPa 90 90 55 62 Method A—100%/min

Tensile Modulus

(MD)

kpsi 310 301 305 385 Instron ASTM D-882-80

MPa 2138 2075 2103 2655 Method A—10% min

Ultimate

Elongation, Min.

(MD)

Instron ASTM D-882-80

% 95 95 90 110 Method A—100%/min

Bursting Strength psi/mil 56.9 48.1 28.9 . 34.7 Mullen

MPa/m 15,446 13,057 7845 .9420 ASTM D-774-67 (1971)

Tear Strength—

Propagating (MD)

g/mil 17.1 19.2 23.1 46.2 Elmendorf

kN/m 6.6 7.4 8.9 17.8 ASTM D-1922-67 (1978)

Tear Strength—

Initial (MD)

g/mil 373 423 333 506 Graves

kN/m 144 163 129 195 ASTM D-1004-66 (1981)

(Continued )


Description

1.0 mil UV Screening

Transparent Type 3

1.0 mil

Transparent

Type 3

1.5 mil Low

Gloss White

Type 3

2.0 mil Satin

White Type 3

Designation Units TUT10BG3 TTR10BG3 TWH15BL3 TWH20BS3 Test Method

Tear Strength—

Initial(TD)

g/mil 435 478 264 377 Graves

kN/m 168 185 102 146 ASTM D-1004-66 (1981)

Impact Strength in lb/mil 20.3 17.5 9.6 16.1 Spencer

kJ/m 90.3 77.9 42.7 71.6 ASTM D-3420-80

Specific Gravity — 1.37 1.39 1.46 1.71 ASTM D-1505-68 (1979)

Coefficient of

Friction Film/Metal

— 0.21 0.21 0.18 0.18 ASTM D-1894-78

Coefficient of

Abrasion

— — — 385 — ASTM D-658-81

Moisture

Absorption

% , 0.5 , 0.5 , 0.5 , 0.5 ASTM D-570-81

Moisture Vapor

Transmission

g/m2d 30.1 30.2 24.5 16.9 ASTM E-96E-80

Thermal Properties

Aging in Air Hours to

embrittlement

3000 3000 3000 3000 Oven at 300�F

Linear Coefficient

of Expansion

(MD)

m/mk 7.8310�5 8.83 1026 6.731025 9.731026 D-696-79 (at 50�70�C)

Linear Coefficient

of Expansion (TD)

m/mk 8.131025 7.13 1025 8.031025 8.331025

Shrinkage, Max.

(TD)

% at �C 6 at 150 5 at 170 5 at 170 5 at 170 ASTM D-1204-78

Specific Heat cal/g �C 0.42 0.24 0.26 0.25 DuPont 990

kJ/kg κ 1.76 1.01 1.09 1.05 Thermal Analyzer

Table 7.3 Typical Properties of Unoriented Grades of Tedlars SP PVF Films [22]

Test Method

Units S.I.

(English)

0.5 mil

Transparent

Medium Gloss

TTR5JAM9

1.0 mil

Transparent

High Gloss

TTR10AH9

1.0 mil UV

Screening

High Gloss

TUA10AH9

1.0 mil

Colored

High Gloss

TXX10AH9

PHYSICAL Tensile Strength ASTM D882-80

Method A�100%

MPa (kpsi) 34 (5) 41 (6) 41 (6) 34 (5)

Tensile Modulus ASTM D882-80

Method A�10%

MPa (kpsi) — — — —

Elongation�Ultimate ASTM D882-80 % 175 200 200 100

Tear Strength, MD ASTM D1004,

Graves

kN/m

(g/mil)

550 (212) 550 (212) 550 (212) 550 (212)

Tear Strength, TD ASTM D1004,

Graves

kN/m

(g/mil)

550 (212) 550 (212) 550 (212) 550 (212)

Unit Weight ASTM D1505-68 g/m2 17.5 35 42�46 34�43

Coefficient of

Friction Film/Metal

ASTM D1894 — 0.21 — —

Falling Sand

Abrasion

ASTM D968 L — 234 — —

Moisture Absorption ASTM D570 % — 0.5 — —

Moisture Vapor

Transmission

ASTM E96E-80 g/m2 � d — 30 — —

Refractive Index ASTM D542-50 — 1.46 — —

Gloss 85 Gardner 31 93 93 93



Haze, Internal Gardner 2 0.6 1.7 —

Haze, Total Gardner 33 2.6 1.4 —

THERMAL Linear Coefficient of

Expansion, MD

D696-79 n/m � K — 9 • 1025 — —

Linear Coefficient of

Expansion, TD

D696-79 m/m � K — 9 • 1025 — —

Shrinkage, Max. ASTM D1204-78 % at 170 C 2 2 2 2

Specific Heat DuPont 990 cal/g � C — 0.24 — —

kJ/kg � K — 1.01 — —

Temperature Range

Continuous Use C 272 to 107 272 to 107 272 to 107 272 to 107

Short Cycle C Up to 175 Up to 175 Up to 175 Up to 175

ELECTRICAL Dielectric Constant ASTM D151-81 7

Dielectric Strength ASTM D151-81 (V/mil) 3000

Dissipation Factor ASTM D151-81 % 0.2

Volume Resistivity ASTM D257-7B ohm/cm 4 • 1013

CHEMICAL

RESISTANCE

Acids 2 hr boiling No Visible

Effect

Bases Immersion No Visible

Effect

(Continued )


Test Method

Units S.I.

(English)

0.5 mil

Transparent

Medium Gloss

TTR5JAM9

1.0 mil

Transparent

High Gloss

TTR10AH9

1.0 mil UV

Screening

High Gloss

TUA10AH9

1.0 mil

Colored

High Gloss

TXX10AH9

Vapor Permeability ASTM E96-80 Mod. g/(100 m2)

(h)(mil)

Acetic Acid ASTM E96-80 Mod. — 45 — —

Acetone ASTM E96-80 Mod. — 10000 — —

Benzene ASTM E96-80 Mod. — 90 — —

Carbon

Tetrachloride

ASTM E96-80 Mod. — 50 — —

Ethyl Acetate ASTM E96-80 Mod. — 1000 — —

Ethyl Alcohol ASTM E96-80 Mod. — 35 — —

Hexane ASTM E96-80 Mod. — 55 — —

Water ASTM E96-80 Mod. — 22 — —

Weatherability Atlas

Weatherometer

Excellent Excellent Excellent

Table 7.4 Chemical Resistance of Polyvinyl Fluoride to Select Organic and Inorganic Chemicals [24]

Exposure Medium Exposure Time Exposure Temperature Exposure Note

Glacial Acetic Acid One Year Room Temperature No Change

Hydrochloric Acid (10% & 30%) One Year Room Temperature No Change

Hydrochloric Acid (10%) One Year Room Temperature No Change

Nitric Acid (20%) One Year Room Temperature No Change

Nitric Acid (10% & 40%) One Year Room Temperature No Change

Phosphoric Acid (20%) One Year Room Temperature No Change

Sulfuric Acid (20%) One Year Room Temperature No Change

Sulfuric Acid (30%) One Year Room Temperature No Change

Ammonium Hydroxide (12% & 39%) One Year Room Temperature No Change

Ammonium Hydroxide (10%) One Year Room Temperature No Change

Sodium Hydroxide (10%) One Year Room Temperature No Change

Sodium Hydroxide (10% & 54%) One Year Room Temperature No Change

Acetone One Year Room Temperature No Change

Benzene One Year Room Temperature No Change

Benzyl Alcohol One Year Room Temperature No Change

Dioxane (14) One Year Room Temperature No Change

Ethyl Acetate One Year Room Temperature No Change

Ethyl Alcohol One Year Room Temperature No Change

(Continued )


Exposure Medium Exposure Time Exposure Temperature Exposure Note

n-Heptane One Year Room Temperature No Change

Kerosene One Year Room Temperature No Change

Methyl Ethyl Ketone One Year Room Temperature No Change

Toluene One Year Room Temperature No Change

Trichloroethylene One Year Room Temperature No Change

Phenol One Year Room Temperature No Change

Phenol (5%) One Year Room Temperature No Change

Sodium Chloride (10%) One Year Room Temperature No Change

Sodium Sulfide (9%) One Year Room Temperature No Change

Tricresyl Phosphate One Year Room Temperature No Change

Glacial Acetic Acid 31 days 75�C No Change

Hydrochloric Acid (10% & 30%) 31 days 75�C No Change

Hydrochloric Acid (10%) 31 days 75�C No Change

Nitric Acid (20%) 31 days 75�C No Change

Nitric Acid (10% & 40%) 31 days 75�C No Change

Phosphoric Acid (20%) 31 days 75�C No Change

Sulfuric Acid (20%) 31 days 75�C No Change

Sulfuric Acid (30%) 31 days 75�C No Change

Ammonium Hydroxide (12% & 39%) 31 days 75�C No Change

Ammonium Hydroxide (10%) 31 days 75�C No Change

Sodium Hydroxide (10%) 31 days 75�C No Change

Sodium Hydroxide (10% & 54%) 31 days 75�C No Change

Acetone 31 days 75�C No Change

Benzene 31 days 75�C No Change

Benzyl Alcohol 31 days 75�C No Change

Dioxane (14) 31 days 75�C No Change

Ethyl Acetate 31 days 75�C No Change

Ethyl Alcohol 31 days 75�C No Change

n-Heptane 31 days 75�C No Change

Kerosene 31 days 75�C No Change

Methyl Ethyl Ketone 31 days 75�C No Change

Toluene 31 days 75�C No Change

Trichloroethylene 31 days 75�C No Change

Phenol 31 days 75�C No Change

Phenol (5%) 31 days 75�C No Change

Sodium Chloride (10%) 31 days 75�C No Change

Sodium Sulfide (9%) 31 days 75�C No Change

Tricresyl Phosphate 31 days 75�C No Change

Table 7.5 Stain Resistance of Polyvinyl Fluoride Films [23]

Staining Agent TTR20SG4 Glossy TWH15BL3 Delustered

Iodine “Lestoil” (full strength) Dry towel

Grape Juice Damp towel Damp towel

Grease “Lestoil” (full strength) “409” all-purposecleaner

Ink, Carter’sBlack

“409” all-purposecleaner

Methylene chloride

Note: Staining agents were applied to the film, allowed to dry for 24 hr, and then removed. Above

are the strongest methods required to completely remove these stains.

100

7

6

5

300

200

100

500 1000Hours in 100ºC (212ºF) steam

%

200

300

Flex life

(a)

(b)

(c)

Impact strength*

Elongation

Fle

x cy

cles

× 1

0–3

kg-c

m/m

il

Figure 7.2 Hydrolytic stability of polyvinyl fluoride: (a) flex life to fatigue

failure; (b) impact strength; and (c) elongation at break [21].


buildings, awnings and signs, and automotive exteriors. Transparent grades of

PVF film are basically transparent to solar radiation in the near ultraviolet, visi-

ble, and near infrared ranges of the light spectrum. Ultraviolet absorbing types

of PVF films protect substrates against ultraviolet light attack (Figure 7.3).

The refractive indexes of PVF and other fluoropolymer films are provided

in Figure 7.4 and Table 7.6. UT grade is opaque ultraviolet-opaque transpar-

ent PVF film, and TR is the transparent grade of PVF including resistance to

UV. Increase in fluorine content of the fluoropolymer decreases its refractive

index; thus, FEP and PFA have the lowest index values. Haze of PVF and

other fluoropolymer films versus light wave length is given in Figure 7.5.

The fluoropolymers in this figure are semicrystalline materials, but only films

of PVF (UT20BG3) and ethylene tetrafluoroethylene copolymer exhibit sig-

nificant haze. Fluorinated ethylene propylene copolymer, perfluoroalkoxy

polymer, and polyvinyl fluoride TR10AH9 films are very clear and show

much less haze than the UV-opaque Tedlars grade [25].

7.6 Thermal Properties

Polyvinyl fluoride performs well in temperatures ranging from approxi-

mately �72�C to 107�C (�98�F to 225�F), with intermittent short-term

1 mil Transparent Tedlar ®PVF Film—TTR10BG3

1 mil UV Opaque, transparentTedlar ® PVF Film—TUT10BG1

Infra-red

Visiblerange

Ultra-violet

20

0 0.2 0.4 0.6 0.8

Wavelength, µm*

1.0 1.2

40

Tra

nsm

issi

on, % 60

80

100

1/8 in Thick window glass

Figure 7.3 Spectral transmission of polyvinyl fluoride [23].


peaking up to 204�C (400�F). Figure 7.6 shows the effect of thermal aging

on mechanical properties of polyvinyl fluoride films when aged at 149�C(300�F). These properties include tensile strength, elongation at break, impact

strength, and flex life to fatigue failure.

Figure 7.7 illustrates the effect of temperature on mechanical properties of

polyvinyl fluoride films, including tensile strength, elongation at break, and

tensile modulus.

1.8

1.7

1.6

1.5

1.4

1.3150 350 550 750 950

Wavelength (nm)

Inde

x of

ref

ract

ion

“n”

1.8

1.7

1.6

1.5

1.4

1.3

Inde

x of

ref

ract

ion

“n”

Wavelength (nm)

1150 1350 1550

150 170 190 210 230 250 270 290

Tedlar® TR10AH9Teflon® ETFE

Tedlar® UT20BG3Teflon® FEP

Teflon® PFA

Figure 7.4 Refractive index of fluoropolymer films as a function of light

wavelength [25].

Table 7.6 Refractive Index of Fluoropolymer Films at d-line at 589.3 nm (LightWavelength) [25]

FP

Tedlar�

PVFUT20BG3

Tedlar�

PVFTR10AH9

Teflon�

ETFETeflon�

FEPTeflon�

PFA

n atD-line

1.474 1.478 1.398 1.350 1.343

PVF5Polyvinyl fluoride (41% by weight fluorine).

ETFE5Ethylene tetrafluoroethylene copolymer (59 % by weight fluorine).

FEP5Perfluorinated ethylene propylene copolymer (76% by weight fluorine).

PFA5Perfluoroalkoxy polymer (76% by weight fluorine).

UT grade is ultraviolet (UV) opaque transparent PVF film.

TR is the transparent grade of PVF (transparent to UV.)


7.7 Electrical Properties

Polyvinyl fluoride films have electrical properties that are of interest in some

applications such as electrical insulation. These characteristics include a high

dielectric constant and high dielectric strength, as shown in Figures 7.8 through

7.11. The excellent thermal aging properties and chemical resistance of Tedlars

offer many functional contributions in a wide variety of applications.

Table 7.7 shows the typical electrical properties of clear and pigmented

Tedlars films. TST20BG4 is a 2 mil (50 μm) thick, Type 4, clear glossy

film; and TWH20BS3 is a 2 mil (50 μm) thick, Type 3, white film with a

satin finish.

The dielectric strength of PVF film varies with film thickness, as shown in

Figure 7.12, and ranges from 2000 to 5000 volts/mil. It is essentially the

same for transparent and colored varieties.

7.7.1 Piezoelectric and Pyroelectric Properties

PVF is one of the few materials that have unusual and interesting properties

called piezoelectricity and pyroelectricity. The direct piezoelectric effect was dis-

covered when electric charges were created by mechanical stress (pressure) on

the surface of tourmaline crystals. A concomitant property of piezo-crystals and

piezo-materials is pyroelectricity, which is defined as the ability of certain mate-

rials to generate a temporary voltage when they are heated or cooled [28].

Tourmaline is an inorganic mineral that occurs naturally with a formula of:

ðNa11 ;Ca21ÞðLi11;Mg21;Al31Þ ðAl31; Fe31;Mn31Þ6ðBO3Þ3ðSi6O18Þ ðOHÞ4:

50%

40%

30%

20%

10%

0%380 480 580

Wavelength (nm)

Haz

e

680 780

Tedlar® TR10AH9 1 mil

Teflon® ETFE 5 mil

Tedlar® UT20BG3 2 mil

Teflon® FEP 5 mil

Teflon® PFA 5 mil

Figure 7.5 Haze of fluoropolymer films as a function of light

wavelength [25].


250

200

150

100

50

5

4

3

2

1

100

10

1

0.1500 1000 1500

Hours in 149ºC (300ºF) air

%10

20

Tensile strength

(a)

(b)

(c)

(d)

Elongation

Impact strength*

Flex life

psi ×

10–3

kg-c

m/m

ilF

lex

cycl

es ×

10–3

Tedlar ® 2

Tedlar ® 3pigmented


Tedlar ® 2


Tedlar ® 2


Tedlar ® 2

Figure 7.6 Effect of thermal aging on mechanical properties of polyvinyl

fluoride films: (a) tensile strength; (b) elongation at break; (c) impact strength;

and (d) flex life to fatigue failure (Tedlars 2 is more oriented than Tedlars 3)

[21].


Other natural inorganic crystals, man-made ceramics and a few polymers

including polyvinylidene fluoride (PVDF) and polyvinyl fluoride (PVF), polyte-

trafluoroethylene (PTFE), and polyvinyl chloride (PVC) have been found to have

piezoelectricity and pyroelectricity properties. Nearly all pyroelectric polymers

are semicrystalline except PVC, which is not crystalline. In spite of noncrystalli-

nity, PVC has relatively high piezoelectric and pyroelectric coefficients.

300

200

100

500

100

10

0(–18)

50(10)

100(38)

200(93)

Temperature, ºC (ºF)

300(149)

%

10

5

15

25

20

Tensile strength

(a)

(b)

(c)

Elongation

Tensile modulus

psi ×

10–3

psi ×

10–3


Tedlar ® 2 & 4

Tedlar ® pigmented

Tedlar ® 4

Tedlar ® 2


Tedlar ® 4

Tedlar ® 2

Figure 7.7 Effect of temperature on mechanical properties of polyvinyl

fluoride films: (a) tensile strength; (b) elongation at break; and (c) tensile

modulus [21].


The most common piezoceramic is lead zirconate titanate (PZT) [chemical

notation: Pb(Zr, Ti)O3], and its piezopolymer counterpart is polyvinylidene fluo-

ride (PVDF). Table 7.8 lists piezoelectric/pyroelectric materials and the respec-

tive coefficients for these properties. When the coefficients of PVF are compared

with those of other polymers in Table 7.8, it is evident polyvinyl fluoride has

fairly weak piezoelectric and modestly strong pyroelectric properties.

140ºC

Dielectric constant—Tedlar ® TST20BG4 vs.frequency at various temperatures

Die

lect

ric c

onst

ant

100ºC

50ºC

23ºC

100 1000 10,000 100,000 1,000,000

Frequency, Hz(Log scale)

789

1011121314151617181920

Figure 7.8 Dielectric constant versus frequency at various temperatures [26].

140ºC

Dissipation factor—Tedlar ® TST20BG4 vs.frequency at various temperatures

Dis

sipa

tion

fact

or

100ºC

50ºC

23ºC

100 1000 10,000 100,000 1,000,000


0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

Figure 7.9 Dissipation factor versus frequency at various temperatures [26].


Some of the applications of piezoelectric materials include the following:

1. Inkjet print heads

2. Optical switches

3. Actuators

4. Accelerometers

140ºC

Dielectric constant—Tedlar ® TWH20BS3 vs.frequency at various temperatures

Die

lect

ric c

onst

ant

100ºC

50ºC

23ºC

100 1000 10,000 100,000 1,000,000


789

1011121314151617181920

Figure 7.10 Dielectric constant versus frequency at various temperatures [26].

140ºC

Dissipation factor—Tedlar ® TWH20BS3 vs.frequency at various temperatures

Dis

sipa

tion

fact

or

100ºC

50ºC

23ºC

100 1000 10,000 100,000 1,000,000


0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

Figure 7.11 Dissipation factor versus frequency at various temperatures [26].


5. Level/flow detectors

6. Micro-positioners

7. Therapeutic medical ultrasound

8. Diagnostic medical ultrasound

9. Hydrophones

Applications of pyroelectric materials include the following:

1. Low weight vibrational sensor

2. Low weight accelerometer

Table 7.7 Examples of Electrical Properties of Commercial Tedlars Film [26]

Property TST20BG4 TWH20BS3 Test Method

Volume resistivity, Ω.cm

At 23�C (73�F) 1.83 1014 6.93 1013 D257-78

At 100�C (212�F) 7.43 1018 1.93 1011

Surface resistivity, Ω/square

At 23�C (73�F) 6.13 1015 1.63 1015 D257-78

At 100�C (212�F) 7.23 1011 1.63 1012

Short-term dielectric strength

DC � V/mil 3700 3200 D149-81

AC � RMS V/mil 2100 1800

5

4

3

2

1

0.5 1.0 2.0 3.0 4.0

Thickness, Mils

Vol

ts/M

il ×

10–3

Figure 7.12 PVF 6 lm dielectric strength at 25�C [27].


3. Pressure or force sensor

4. Mechanical deformation transducer

5. Temperature transducer

6. Infrared sensor

7. Imaging device-pyrometer

8. Flowmeter

9. Water vapor sensor

10. Micro-motion sensor

11. Semiconductor integrated FET sensor

12. Event counter

13. Ultrasonic detection of failures in metals or plastics

Table 7.8 Piezoelectric and Pyroelectric Constants (d31) of VariousMaterials [29]

Material Material Structure

PiezoelectricCoefficient,pC/N

PiezoelectricCoefficient,µC/K.m2

Polymers

PVDF 2CF22CH22CF22CFH2(β-phase)

20�30 30�40

PVDF δ-phase 10�17 10�15

VDF-TriFE 2CF22CH22CFH2CF22 15�30 30�40

PVF 2CH22CFH2CH22CFH2 1 10

PVC CH22CClH2CH22CClH2 1 1�3

Nylon 11 (γ-phase) 3 3

Ceramics

Lead zirconatetitanate

Pb[ZrxTi(12x)]O3

0# x# 1)100�300 50�300

Barium titanate BaTiO3 80 200

Quartz SiO4 (silicon�oxygentetrahedral)

2


7.8 Weathering Performance

Weathering resistance, or weatherability, refers to the resistance of polyvinyl

fluoride to degradation by sunlight in combination with other elements of climate.

The outdoor durability of PVF is among the characteristics discovered early in

the development this polymer. Most plastics degrade in outdoor environments,

exhibited by fading, deterioration of mechanical properties and being abraded.

PVF was found to possess outstanding resistance to all elements of the outdoor

climate. All key properties of PVF are retained to a significant extent after years

of exposure, even in challenging environments such as Florida. Thus, polyvinyl

fluoride became a coating of choice for siding and cladding on the exterior of

buildings and other objects such as radomes (a radome is a dome that protects

radar equipment, usually made from material transparent to radio waves).

Decorative requirements of architectural designs are met by the availability of

PVF films in a variety of colors. Durable pigments have been used to manufac-

ture a vast number of colors and appearances of PVF films. The inside surfaces

of PVF films are treated to render them bondable using adhesives. These films

are laminated to a variety of substrates, including metal, plastic, and wood, thus

imparting a long serviceable life to the substrate. Most colors exhibit no more

than 5 NBS units (Modified Adams Color Coordinates) color change after 20

years of vertical exposure outdoors.

There are two ways of testing the weather resistance of materials that include

plastics: outdoors and accelerated. Outdoors testing requires placement of

numerous samples outdoors under well-defined exposure conditions, typically

according to ASTM D1435-05. Periodically, samples are removed to measure

the properties of interest. The results of outdoor weathering of plastics represent

the closest outcome to what may be expected in an outdoors application.

Locations are usually selected according to the latitude and the prevailing

climate. The biggest drawbacks to outdoor testing are the length of time and cost.

The American Society for Testing Materials defines accelerated weather-

ing as follows:

The exposure of plastics to cyclic laboratory conditions involving

changes in temperature, relative humidity and ultraviolet (UV) radiant

energy, with or without direct water spray, in an attempt to produce

changes in the material similar to those observed after long-term con-

tinuous outdoor exposure.

Accelerated weathering machines have been devised for a long time to

mimic the action of sunlight and the elements. The early machines used car-

bon arc, which was replaced by Xenon arc and ultraviolet lamps in newer

apparatus. The most popular of these machines are called by their trade


names Weather-O-Meters, Xenotests (by Atlas Material Testing Solutions),

and QUVs Weathering Tester (by Q-Lab). To date, no machine has been

found that completely duplicates the natural light and climate conditions

because of the complexity and unpredictability of the natural weather ele-

ments. The correlation between outdoor performance of plastics and weather-

ing tests is inexact. The biggest benefit of accelerated testing in machines is

in comparison of types of plastics and other variables in formulation of a

given plastic such as PVF. Machine data are useful in characterizing the

weatherability of plastics and differentiation of different materials.

Weatherability of polyvinyl fluoride films has been studied in outdoor

environments and under accelerated conditions. The popular locations for

weathering in the United States are stations in south Florida and Arizona

because of the intensity of the sun and humidity in the case of Florida.

Unsupported transparent PVF has retained at least 50% of its tensile strength

after 10 years in Florida facing south at 45�. Color stability, Weather-O-

meter, and Florida exposure are shown in Figures 7.13 through 7.15.

The darkness-lightness of film color affects the temperature that the film

experiences; the higher the temperature, the higher the rate of degradation.

Temperature of the exposed film is an important consideration is signage and

awnings. Figure 7.16 shows temperature increase (over ambient temperature)

5

4

3

2

1

01000 2000 3000 4000 5000

Hours

Note: Colored films vary slightly in color retention, depending on color.

E—

NB

S u

nits

Figure 7.13 Color stability: accelerated exposure using a carbon arc (Atlas

Sunshine Arc Weather-Ometer) [23].


of vinyl siding substrate coated with a color polyvinyl fluoride film as a

result of exposure in a moderate climate. Darker colors such as brown and

gray can reach as much as 39�C (70�F) hotter than the ambient temperature

when exposed at a 45� angle, whereas the surface temperature of light colors,

such as white, under identical conditions may reach only 11�C (20�F)over ambient temperature; and dark colors at a 45� exposure angle can be as

100

80

60

40

20

0

% o

f ini

tial p

rope

rtie

sre

tain

ed

1 2 3 4 5 6

Years

Elongation

Tensile

Figure 7.15 Physical property retention of PVF film: Florida exposure (45�

facing south) [23].

100

80

60

40

20

02000 4000 6000 8000

Hours

% o

f ini

tial p

rope

rtie

sre

tain

ed

Tensile

Elongation

Figure 7.14 Accelerated exposure of PVF film using carbon arc (Atlas

Sunshine Arc Weather-O-meter) [23].


much as 11�C (20�F) hotter than those at a vertical angle, whereas light col-

ors at a 45� angle may be only several degrees more than those at a vertical

angle [30].

Adding color pigments or ultraviolet (UV) ray absorbers to PVF films pro-

tects the components behind them differently than colored films. The pig-

ments in colored PVF films act as blockers to UV and visible light and are

longer lasting than are the additives used to screen out UV light in the trans-

parent films. Because the clear films do not contain pigments, they rely on

these special additives to help keep harmful UV light from affecting the film

and the adhesive.

There are transparent grades of Tedlars PVF films that contain UV block-

ers. Clear PVF film with UV absorber additives initially blocks greater than

99% of the UV light over the energy wavelength range of 290�350 nm.

Lower energy light in the range of 350�400 nm is blocked to a lesser extent

by the film. As with all other transparent films, the UV screening film trans-

mits visible light.

The UV absorber additives in PVF film do not endure permanently. After

a period of time, these absorbers are gradually depleted, and the more

destructive, higher energy light is allowed to pass through the film. Studies

of free-standing, 1 mil thick, UV-screening Tedlars film grade TUT10BG3

weathered in south Florida at a 45� angle facing south indicate that under

these conditions, the UV absorbers will be slightly less than 50% depleted

after 5 years (see Figure 7.17). The rate of depletion of UV absorber may

80

70

60

50

40

30

2020 30 40 50 60 70 80 90 100

Tem

pera

ture

incr

ease

ove

r am

bien

t, ºF Vertical angle exposure

45º Angle exposure

Increasing film color lightness

Figure 7.16 Temperature increase of vinyl laminates surfaced with PVF film

versus film darkness [30].


increase when the film is laminated to a substrate. A laminate reaches a high-

er temperature than a free-standing film. This difference in temperature can

accelerate the degradation of the UV absorber.

Uncoated and unclad vinyl fabrics show a different weathering pattern.

The appearance of these fabrics deteriorates gradually, typically manifesting

by loss of gloss and accumulation of dirt (see Figure 7.18). A material that

loses gloss will appear lighter and less colorful to the eye. Vinyl that is

embedded with dirt also will appear less colorful. The benefit of PVF film is

100

80

60

40

20

00 2 4 6 8 10

Florida exposure (Years): 45º Angle, south facing

Initi

al a

bsor

banc

e (a

t 360

nm),

%

Figure 7.17 Average rate of UV absorber degradation in free-standing

Tedlars PVF film (TUT10BG3) exposed in Florida [30].

80

100

60

40

20

00 1 2 3 4 5

Years

60º

Glo

ss r

eten

tion,

%

TUT10BG3 Tedlar ® filmPigmented vinyl

Figure 7.18 Percent gloss retention in south Florida weathering at 45� anglesouthern exposure [30].


that once it becomes dirty, the initial appearance can be restored easily, with-

out harsh chemicals.

7.9 Description of Available Product andProperties of Unoriented PVF Films

The trade name of unoriented PVF film is Tedlars SP (by DuPont). This

family of products possesses a few major attributes. First, it is manufactured

by web coating on a carrier film. Second, multilayer adhesive-free films can

be produced to replace adhesive-bonded laminates in some end uses. Third, it

is much easier to manufacture thin PVF films using SP technology.

Following the cure of PVF coating and the finishing steps, PVF film is

removed from the carrier. Some of the manufacturing steps, such as slitting

and surface treatment for adhesion, are facilitated by the presence of the

carrier. Presence of a PVF carrier is even useful for some applications such

as laminations in which the PVF surface must be protected [22].

The unoriented PVF films are used in a variety of parts, including aircraft

interiors, signs, awnings, body side moldings, wall coverings, architectural

panels, and thermoplastic laminates. Unoriented PVF film has been manufac-

tured in a broad range of colors and thicknesses including those required for

aircraft interior walls and ceilings [22].

Table 7.3 presents the properties of a few single-layer Tedlars SP PVF films.

7.9.1 Physical/Thermal Properties

In spite of minimal orientation, unoriented PVF films are strong, flexible,

and fatigue-resistant. Their resistance to failure by flexing is outstanding.

They performs well in temperatures ranging from approximately �73�C to

107�C (�100�F to 225�F), with intermittent short-term peaking up to 204�C(400�F). Figures 7.19 through 7.23 show a number of properties of unor-

iented PVF films as a function of temperature.

7.9.2 Chemical Properties

Unoriented PVF films have excellent resistance to chemicals, solvents,

and stains. They retain strength even when exposed to strong acids and bases.

At ordinary temperatures, unoriented PVF film is not affected by many

classes of common solvents, including hydrocarbons and chlorinated

solvents. It is resistant to greases and oils.


7.9.3 Electrical Properties

Properties of interest to the electrical industry include hydrolytic stability,

high dielectric strength, and relatively low dielectric constant. The excellent

thermal aging properties and chemical resistance of unoriented PVF films

offer many functional contributions in a wide variety of applications.

7.9.4 Optical and Spectral Properties

Transparent types of unoriented PVF films are essentially transparent to

solar radiation in the near-ultraviolet, visible, and near-infrared regions of the

spectrum. Ultraviolet-absorbing types of Tedlars SP are useful for protecting

various substrates against ultraviolet light attack (Figure 7.24).

2.0

1.5

1.0

0.5

0.050 75 100 125 150

Temperature, ºC

Shr

inka

ge, %

TUA10AH91 Mil colored filmsTTR10AH9TTR5JAM9

Figure 7.19 Shrinkage of unoriented PVF films as a function of temperature

(held for 30 minutes at the indicated temperature) [22].

400

350

300

250

200

150

100

50

020 40 60

Temperature, ºC

Elo

ngat

ion

at b

reak

, %

80 100

MD-TTR10SH9

MD-TUA10AH9TD-TUA10AH9TD-TTR5JSH9MD-TTR5JSH9

TD-TTR10SH9

Figure 7.20 Break elongation of clear, unoriented PVF films as a function of

temperature [22].


6.0

5.5

5.0

4.5

4.0

3.5

3.0

2.0

2.5

1.520 40 5030 60 70

Temperature, ºC

Ten

sile

str

engt

h, k

psi

80 90 100

TD-TTR10SH9

TD-TTR5JSH9TD-TUA10AH9MD-TUA10AH9MD-TTR5JSH9

MD-TTRJ10SH9

Figure 7.21 Tensile strength of clear, unoriented PVF films as a function of

temperature [22].

400

350

300

250

2000 10 20 30

Temperature, ºC

Elo

ngat

ion

at b

reak

, %

40 50

Figure 7.22 Break elongation of pigmented unoriented PVF films as a

function of temperature [22].

8

6

7

5

4

3

2

120 40 60

Temperature, ºC

Ulti

mat

e te

nsile

str

engt

h, k

psi

80 100

Figure 7.23 Tensile strength of clear, unoriented PVF films as a function of

temperature [22].


7.9.5 Weather Resistance

Accelerated weathering tests on unoriented PVF films have been conducted

using a variety of test methods. The weather resistance, inertness, and tough-

ness characteristics allow for broad use as a surface protection for metals,

hardboards, felts, or plastics in architectural, decorative, or industrial applica-

tions. Pigmented Tedlars SP, properly laminated to a variety of substrates,

imparts a service life significantly longer than that of conventional finishes.

7.9.6 Formability

Unoriented PVF films are versatile industrial films that can be applied

over a variety of substrates, including Nomexs aramid fiber, polycarbonate,

vinyl fabric, and aluminum. Formable Tedlars SP is manufactured in 0.5,

1.0, and 2.0 mil thicknesses.

Unoriented PVF film can be stretched over 300%�400% high irregular

shapes when sharp edges on the mold surfaces are avoided. It is recommended

that film thickness and surface temperature be optimized for the depth of draw

and part size. Film-forming surface temperatures from 105�C to 171�C (221�Fto 340�F) allow excellent shape forming. The heat-up time to reach this tem-

perature window is not important. However, it is possible to overheat the film.

To avoid part failure by overheating during forming and to minimize part cost,

the film or laminate surface temperature should not exceed 171�C (340�F).

7.9.7 Surface Aesthetics

Designers will appreciate the wide range of color and gloss options avail-

able with Tedlars SP. Unoriented PVF film can be used alone or in accented

texture color styling. Low-gloss multilayer films have specular gloss in the

3.5

3.0

2.5

2.0

1.5

1.0

0.5

0200 250 300 350 400 450

Wavelength, nm

Abs

orba

nce

500 550 600 650 700

TUA10BG3TUA10AH9TTR10BG3TTR10AH9

Figure 7.24 Ultraviolet light absorbance of clear, unoriented PVF films as a

function of temperature [22].


10%�15% range at 85� Gardner scale. These films are suitable for silk-screen

printing. Medium-gloss films offer specular gloss in the 30%�35% range and

are fit for fabric laminates and automotive trims. High-gloss unoriented PVF

film ranges from 80% to 85% and is intended for striping, lettering, and plastic

laminates. Transparent Tedlars SP is manufactured in high-gloss, medium-

gloss, and low-gloss versions. These products are laminated as a protective

cap sheet over printed or silk-screened graphics to lock in their beauty.

7.9.8 Adhesion

Unoriented PVF film has different surface characteristics. Films are avail-

able as one-side adherable (A), two-side adherable (B), or strippable (S).

Adherable surfaces are used with adhesives for bonding to a wide variety of

substrates. These surfaces have excellent compatibility with many classes of

adhesives, including acrylics, polyesters, epoxies, rubbers, and pressure-

sensitive masses. The strippable surface has excellent release properties for use

as a mold release agent for epoxies, phenolics, rubbers, and other plastic resins.

7.9.9 Ease of Cleaning

Unoriented PVF films exhibit superior stain resistance and ease of clean-

ing. Tedlars SP is resistant to staining agents and will not fade or streak

even after heavy cleaning.

7.9.10 Abrasion Resistance

Comparative testing of aircraft laminate materials clearly demonstrates

superior abrasion resistance of unoriented PVF film over other

commonly used surface materials. This exceptional abrasion resistance makes

it possible to replace heavyweight components in many interior applications.

Table 7.9 presents the results of a study of abrasion of oriented and unoriented

PVF film as a result of outdoor exposure for a few years. The results for both

types indicate excellent retention of thickness after 2�4 years of Florida exposure.

7.10 Effect of Radiation

Polyvinyl fluoride cross-links readily when exposed to ionizing radiation

[31]. Investigation [32] of the tensile properties of PVF showed the elonga-

tion to break to drop from about 200% for the unirradiated polymer to

approximately 20% after a dose of 1000 kGy. Tensile strength also dropped

significantly, indicating predominant cross-linking. The tensile properties

of PVF were investigated in other studies [33], which also concluded


cross-linking. Irradiation doses were relatively small (max. 200 kGy), but

there was an observed decrease in the elongation to break.

Wall et al. [34,31] investigated the swelling and sol/gel ratios of PVF.

PVF films of 4 mm thickness were g-irradiated in a vacuum. The important

radiolytic reaction was that HF split off. Similar to polyvinylidene fluoride,

the rates of thermal volatilization of HF were observed to increase for PVF

samples that had been previously irradiated.

Table 7.9 Effect of Outdoor Weathering on PVF Film [27]

Film ExposureThickness,in.

AbrasionResistance,min./min FilmThickness

Retentionof Gloss(20�), %Initial Aged

UnorientedPVF

— 0.0042 4.8 4.1 74

4 yr. inFlorida

0.0037 4.6 4.2 —

OrientedPVF

— 0.0015 3.4 3.0 75

2 yr. inFlorida

0.0016 2.9 2.2 80

–150 –160 –170 –180 –190 –200 –210 –220 –230 –240

i

h, ed, g

c

a

b

f

Figure 7.25 Solution-state 1H-decoupled 19F NMR spectrum of polyvinyl

fluoride dissolved in dimethyl formamide-d7 [35].


7.11 NMR Spectrum of Polyvinyl Fluoride

Figure 7.25 shows a solution-state 1H-decoupled 19F NMR spectrum of

polyvinyl fluoride dissolved in dimethyl formamide-d7 obtained by Ando et al.

[35]. Based on work by Bruch et al. [36], they made assignment to peak sig-

nals, in Figure 7.25, of the solution-state 19F spectrum of commercial PVF and

of samples synthesized in the laboratory. The assignments were based on

inversions or defects in PVF molecules that consist of head-to-head and tail-

to-tail bonds (see Section 7.2 in this chapter).

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