ASTM D3222-99

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
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Designation: D 3222 – 99
Standard Specification for
Unmodified Poly(Vinylidene Fluoride) (PVDF) Molding
Extrusion and Coating Materials
This standard is issued under the fixed designation D 3222; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.
Information in this specification is technically equivalent to related
1. Scope *
information in ISO 12086-1 and ISO 12086-2.
1.1 This specification covers melt processable molding and
extrusion materials, as well as coating materials of poly(vi-
2. Referenced Documents
nylidene fluoride) fluoroplastic, commonly abbreviated PVDF
2.1 ASTM Standards:
(or PVF in scientific literature). This specification covers
D 149 Test Method for Dielectric Breakdown Voltage and
thermoplastic resin materials supplied in pellet or powder
Dielectric Strength of Solid Electrical Insulating Materials
form.
at Commercial Power Frequencies
1.2 This specification applies only to the virgin homopoly-
D 150 Test Methods for A-C Loss Characteristics and
mer prepared from vinylidene fluoride, not copolymers, rein-
Permittivity (Dielectric Constant) of Solid Electrical Insu-
forced, filled grades or special grades with additives or
lating Materials
treatments for modification of attributes.
D 256 Test Methods for Impact Resistance of Plastics and
1.3 The tests involved are intended to provide information
Electrical Insulating Materials
for specification of unmodified PVDF homopolymer resins. It
D 257 Test Methods for D-C Resistance or Conductance of
is not the purpose of this specification to provide engineering
Insulating Materials
data for design purposes.
D 542 Test Methods for Index of Refraction of Transparent
1.4 PVDF fluoroplastics melt between 156 and 180°C (312
Organic Plastics
and356°F)andarethermallystableuptoabout370°C(698°F).
D 618 Practice for Conditioning Plastics and Electrical
NOTE 1—Warning: Evolution of corrosive and toxic hydrogen fluoride Insulating Materials for Testing
can occur under certain conditions.
D 638 Test Method for Tensile Properties of Plastics
D 790 TestMethodsforFlexuralPropertiesofUnreinforced
1.5 The values stated in SI units are to be regarded as the
and Reinforced Plastics and Electrical Insulating Materi-
standard. The values given in parentheses are for information
als
only.
D 792 TestMethodsforDensityandSpecificGravity(Rela-
NOTE 2—PVDF exhibits polymorphism. The type and extent of
tive Density) of Plastics by Displacement
crystalline structure varies with the thermomechanical history of the
D 883 Terminology Relating to Plastics
sample. Specimens prepared by techniques different than prescribed in
D 1238 Test Method for Flow Rates of Thermoplastics by
this specification could have properties that may vary from the values
Extrusion Plastometer
specified.
D 1505 Test Method for Density of Plastics by the Density-
1.6 This standard does not purport to address all of the
Gradient Technique
safety concerns, if any, associated with its use. It is the
D 1898 Practice for Sampling of Plastics
responsibility of the user of this standard to establish appro-
D 2863 Test Method for Measuring the Minimum Oxygen
priate safety and health practices and determine the applica-
Concentration to Support Candle-like Combustion of Plas-
bility of regulatory limitations prior to use. Specific precau-
tics (Oxygen Index)
tionary statements are given in Note 1 and Section 10.
D 3295 Specification for PTFE Tubing
NOTE 3—There is no equivalent ISO standard for this specification.
D 3418 Test Method for Transition Temperatures of Poly-
mers by Thermal Analysis
D 3835 Test Method for Determination of Properties of
This specification is under the jurisdiction of ASTM Committee D-20 on
Plastics and is the direct responsibility of Subcommittee D20.15 on Thermoplastic
Materials.
Current edition approved April 10, 1999. Published July 1999. Originally
published as D 3222 – 73. Last previous edition D 3222 – 97. Annual Book of ASTM Standards, Vol 10.01.
2 4
Lovinger, A. J., “Poly(Vinylidene Fluoride)” Developments in Crystalline Annual Book of ASTM Standards, Vol 08.01.
Polymers, Vol 1, Chapter 5, D. C. Bassett, Ed., Applied Science, London, 1982. Annual Book of ASTM Standards, Vol 08.02.
*A Summary of Changes section appears at the end of this standard.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D 3222
Polymeric Materials by Means of a Capillary Rheometer resin grades available from several sources and are provided
D 3892 Practice for Packaging/Packing of Plastics for information purposes only.
D 4895 Specification for Polytetrafluoroethylene (PTFE) 4.1.2 Type II—PVDF fluoroplastics are polymerized in
Resins Produced From Dispersion suspension. Peak melting temperatures of these resins range
E 380 Practice for Use of the International System of Units from 164 to 180°C. The particles isolated from suspension are
(SI) spherical and range typically from 20 to 150 µm in diameter.
2.2 IEC and ISO Standards: 4.1.2.1 Type II resins are available commercially, and the
ISO 12086-1 Plastics—Fluoropolymer Dispersion and data of Table 1 reflect ranges encompassing values typical for
Moulding and Extrusion Materials—Part 1: Designation the properties of available grades.
and Basis for Specification 4.2 A one-line system may be used to specify materials
ISO 12086-2 Plastics—Fluoropolymer Dispersion and covered by this specification. The system uses predefined cells
Molding and Extrusion Materials—Part 2: Preparation of to refer to specific aspects of this specification, as illustrated
Test Specimens and Determination of Properties below.
Specification
3. Terminology
Special
Standard Number Block Type Grade Class
notes
3.1 Definitions:
Example: Specification
3.1.1 For definitions of plastics terms used in this specifi-
D 3222 – 97 I 2 . .
cation, see Terminology D 883.
For this example (D 3222 – 97, I2), the line callout describes
3.2 Abbreviations:Units, Symbols, and Abbreviations:
a PVDF resin polymerized in emulsion, having a specific
3.2.1 For units, symbols and abbreviations used in this
gravity between 1.75 and 1.79, and a peak melting endotherm
specification see Practice E 380.
between 162 to 170°C. A comma is used as the separator
between the Standard Number and theType. Separators are not
4. Classification
needed between the Type, Grade, and Class. Provision for
4.1 This specification covers two types of natural, unmodi-
Special Notes is included so that other information, such as a
fied PVDF fluoroplastics supplied in pellet form for molding
preferred viscosity range, can be provided when required.
andextrusion,andinpowderformforsolutions,dispersions,or
When special notes are used, they should be preceded by a
coatings.
comma.
4.1.1 Type I—PVDF fluoroplastics are polymerized in
emulsion. Depending upon the polymerization conditions, the
5. General Requirements
peak melting point of the resin can be varied between 156 and
5.1 Thematerialshallbeofuniformcompositionandfreeof
170°C. The diameter of the primary particle isolated from the
foreign matter to the contamination level agreed upon between
emulsion is typically less than 1 µm; the dried powder has an
the purchaser and seller.
average agglomerate diameter range of 3 to 15 µm.
4.1.1.1 Two distinctly different Type I emulsion PVDF
6. Detail Requirements
resins are available commercially. These are differentiated by
6.1 General Attributes:
peak melting endotherm values, as shown in Table 1, and this
6.1.1 Peak Melting Endotherm—The material covered by
difference is the basis for subdividingType I resins into Grades
this specification shall have a minimum peak melting endot-
1 and 2.Table 1 shows the melt viscosity ranges encompassing
herm for the type and class as shown in Table 1 when tested in
accordance with Test Method D 3418. For Type I resins, this
shall involve heating a solid specimen of 5 6 1 mg from room
Annual Book of ASTM Standards, Vol 08.03.
7 temperature to 200°C at 10°C/min, maintaining the tempera-
Annual Book of ASTM Standards, Vol 14.02.
Available from American National Standards Institute, 11 W. 42nd St., 13th ture at 200°C for 5 min, followed by cooling at a controlled
Floor, New York, NY 10036.
rate of 10°C/min to about 30°C, then reheating at 10°C/min to
Dohany, J. E., and Robb, L. E., “Poly(Vinylidene Fluoride)” Kirk-Othmer
200°C. Record the peak melting endotherm during the second
Encyclopedia of Chemical Technology, Vol 11, 3rd Edition, 1980, pp. 64–74.
melting cycle.
6.1.1.1 Temperature—Test Type II resins likewise except
TABLE 1 Classification of PVDF Resins
that the maximum is 250°C.
Typical Values or Ranges
6.1.2 Specific Gravity—A solid specimen of the material
Property Type I
covered by this specification shall have the minimum specific
Grade 1 Grade 2 Type II
gravity indicated in Table 1 (1.75 for Type I, Class 1 and 1.76
Specific Gravity 1.75 to 1.79 1.75 to 1.79 1.76 to 1.79
for all others) when tested in accordance with Test Methods
Peak Melting Endotherm, °C 156 to 162 162 to 170 164 to 180
D 792 or D 1505.
A
Apparent Melt Viscosity, Pa·s:
6.1.3 Refractive Index—The material covered in this speci-
High Viscosity 2800 to 3800 2800 to 3100 2500 to 4000
Medium Viscosity 2300 to 2800 1300 to 2800 1300 to 2500
fication shall have a refractive index of 1.42 when measured at
Low Viscosity . 500 to 1300 500 to 1300
A −1
Reported for a shear rate of 100 s determined by capillary rheometry at
232°C (450°F) using 0.027 radian (60°) entrance angle die with L/D of 15 and
See the ASTM Form and Style for ASTM Standards, available from ASTM
accordingtoproceduresofTestMethodD 3835.Multiplythepascalsecondvalues
by ten to obtain poise values. Headquarters.
D 3222
the sodium D line at 25°C (77°F) in accordance with the specimens may be compression-molded and tested after the
refractometer procedure in Test Methods D 542, using speci- conditioning period as specified above.
mens that have not been subjected to any processes which
6.4 Electrical Properties:
induce orientation of the polymer chains or crystal-lites.
6.4.1 D-C Resistance—The material covered in this speci-
Compression-molded specimens at least 2-mm (0.079-in.)
fication shall have a d-c volume resistivity greater than 1.2V·
thick that have been quenched rapidly in water are preferred.
m (1.2 3 10 V·cm) when tested as a 0.76-mm (0.030-in.)
compression-molded specimen (see Section 8) in accordance
6.1.4 Limiting Oxygen Index—The material covered in this
with Test Methods D 257.
specification shall have a minimum limiting oxygen index of
6.4.2 Dielectric Strength—The material covered in this
42 when tested in accordance with Test Method D 2863.
specification shall have a dielectric strength in air no less than
NOTE 4—If a column with a restricted opening is used, the top of the
57 kV/mm (1280 V/0.001 in.) by the “short-time” method of
specimen should be positioned 40 mm below the opening.
Test Methods D 149 with 0.13-mm (0.05-in.) thick
6.2 Processing Related Attributes: compression-molded specimens (see Section 8) tested in air
6.2.1 Flow Rate—Materialsconformingtothisspecification using 25.4-mm (1-in.) Type 3 electrodes.
may be tested for melt flow rate according to Test Method 6.4.3 Dielectric Constant—The material covered in this
D 1238, using 232°C and 21.6-kg load for medium or high specification shall have a dielectric constant less than 11.0 at
melt viscosity grades; low melt viscosity grades may be tested 100 Hz and greater than 7.2 at 1 MHz when tested as a 3.2-mm
at 232°C (450°F) usinga5kg weight. (0.125-in.)thickcompression-moldedspecimen(seeSection8)
according to Test Methods D 150 at 23°C (73°F).
6.2.2 Rheological Properties—The preferred method for
6.4.4 Dissipation Factor—The material covered in this
measuring flow characteristics is capillary rheometry. Thus
specification shall have a dissipation factor of less than 0.045
rheological properties of the materials should be tested accord-
at 100 Hz and less than 0.24 at 1 MHz when tested as 3.2-mm
ing to Test Method D 3835 at 232°C (450°F) using a die with
(0.125-in.) compression-molded specimens (see Section 8)
an entrance angle of 60° (cone angle of 120°) and a minimum
according to Test Methods D 150 at 23°C (73°F).
capillary L/D of 15. See Table 1.
6.3 Mechanical Properties:
NOTE 5—Since this material has very low water-absorption character-
istics, maintenance of constant humidity during testing or specimen
6.3.1 Tensile Properties—The material covered in this
preparation is not necessary except as required for a specific test method.
specification shall have a tensile yield strength exceeding 36
However, no moisture should be present in the resin when preparing
MPa (5200 psi) at 23°C (74°F) and a minimum elongation at
specimens for testing. Heat the resin sample at 110°C (230°F) in an
break of 10 % when tested according to Test Method D 638 at
air-circulating oven until the adventitious moisture is removed.
51 mm (2 in.)/min, using Type I specimens 3.2-mm (0.125-in.)
thick as specified in Test Method D 638. Condition in accor-
7. Sampling
dance with Procedure A of Test Method D 638, except that a
7.1 Materials shall be sampled in accordance with Practice
minimum time of 16 h before testing is satisfactory. Preferably,
D 1898. Adequate statistical sampling shall be considered an
compression-molded samples should be used (see Section 8),
acceptable alternative.
but injection molded specimens may be used, providing that
the samples yield and rupture in the gage region and not near
8. Preparation of Compression Molded Specimens
the heel. Specimens should be molded under conditions speci-
8.1 Equipment:
fied by the resin suppliers. Generally, injection molded speci-
8.1.1 Press with approximately 180 kN (20 ton) capacity
mens show low and variable elongation values compared to
compression-molded specimens. andheatingcapabilityformaintainingplatensbetween220and
240°C (428 to 464°F).
6.3.2 Flexural Properties—The material covered in this
8.1.2 Two smooth chromium-finished plates with approxi-
specification shall have a minimum flexural modulus of 1.38
mate dimensions 150 3 250 3 5 mm (10 3 10 3 0.02 in.), or,
GPa(190 3 10 psi)whentestedaccordingtoMethodIofTest
if more appropriate to the press type, 150 3 150 35mm
Methods D 790, using 6.4-mm (0.25-in.) thick specimens
(6 3 6 3 0.02 in.).
prepared by injection molding under conditions specified by
8.1.3 Flat open-cavity steel molds, that is, frames
...