ASTM D8154-24

Standard Test Methods for ¹H-NMR Determination of Ketone-Ethylene-Ester and Polyvinyl Chloride Contents in KEE-PVC Roofing Fabrics

SIGNIFICANCE AND USE
5.1 Determination of the percentage of KEE compound in sheet roofing is of concern to many specifiers and building owners. Method A, the faster method, is best used for quality control. Method B may apply better to research and development or investigative work.
SCOPE
1.1 This test method pertains to the determination of the relative contents of ketone-ethylene-ester (KEE) and polyvinyl chloride (PVC) after their extraction from reinforced roofing membranes or fabrics. Based on proton nuclear magnetic resonance spectroscopy (1H-NMR), the method allows for the quantification of PVC with respect to an internal standard. The KEE content is then obtained by difference. The test method is not applicable to membranes or blends that contain high molecular weight polymers other than PVC and KEE.  
1.2 Units—The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.  
1.3 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety, health, and environmental practices and determine the applicability of regulatory limitations prior to use.  
1.4 This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.

General Information

• Status: Published
• Publication Date: 31-Dec-2023
• ICS: 91.100.50 - Binders. Sealing materials
• Technical Committee: D08 - Roofing and Waterproofing
• Drafting Committee: D08.18 - Nonbituminous Organic Roof Coverings

Relations

• Replaces: ASTM D8154-17e1 - Standard Test Methods for ¹H-NMR Determination of Ketone-Ethylene-Ester and Polyvinyl Chloride Contents in KEE-PVC Roofing Fabrics
• Effective Date: 01-Jan-2024

Overview

ASTM D8154-24: Standard Test Methods for ¹H-NMR Determination of Ketone-Ethylene-Ester and Polyvinyl Chloride Contents in KEE-PVC Roofing Fabrics provides standardized procedures for analyzing and quantifying the relative contents of ketone-ethylene-ester (KEE) and polyvinyl chloride (PVC) in reinforced roofing membranes or fabrics using proton nuclear magnetic resonance (¹H-NMR) spectroscopy. This test method addresses the need for accurate composition determination of KEE and PVC in sheet roofing products, which is a substantial concern for building owners, specifiers, and manufacturers, particularly for quality control and research purposes.

The methods described are intended to offer reliable measurement and differentiation of these two major polymers within roofing membranes, making them valuable tools for quality assurance, material verification, and technical investigation throughout the roofing industry.

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Key Topics

• Quantitative ¹H-NMR Analysis: Utilizes proton NMR spectroscopy for precise measurement of PVC, with an internal standard, and KEE (by difference).
• Sample Extraction and Purification: Detailed guidance on extraction, purification, and sample preparation to minimize interferences from plasticizers, fillers, or other contaminants.
• Two Analytical Methods:
  • Method A: Fast and effective, ideal for routine quality control.
  • Method B: Incorporates calibration curves, suitable for research, R&D, or investigative purposes where higher precision is required.
• Repeatability and Reproducibility: Includes statistical evaluation to ensure reliability within and across laboratories.
• Scope Limitations: Not intended for blends containing high molecular weight polymers other than KEE or PVC.
• Safety Guidance: Emphasizes safety, health, and environmental considerations due to the use of chemicals and strong magnetic fields.

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Applications

The test methods described in ASTM D8154-24 are highly applicable in several key areas:

• Quality Control: Allows manufacturers to confirm the KEE and PVC ratios in roofing fabrics align with product specifications and contractual requirements.
• Material Verification: Enables building owners and specifiers to independently verify material composition for compliance and performance assurances.
• R&D and Investigative Analysis: Offers researchers and developers accurate tools to analyze polymer blends in new roofing products or to diagnose material failures.
• Regulatory Compliance: Facilitates adherence to required international standards in the production and supply of roofing materials, supporting procurement and regulatory review.
• Interlaboratory Consistency: Provides a foundation for comparative studies and benchmarking across different laboratories, enhancing data confidence.

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Related Standards

For users of ASTM D8154-24, the following ASTM standards and related documents are commonly referenced or applicable:

• ASTM D1079 - Terminology Relating to Roofing and Waterproofing
• ASTM D6754/D6754M - Specification for Ketone Ethylene Ester Based Sheet Roofing
• ASTM E177 - Practice for Use of the Terms Precision and Bias in ASTM Test Methods
• ASTM E691 - Practice for Conducting an Interlaboratory Study to Determine the Precision of a Test Method

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Practical Value

Adopting ASTM D8154-24 ensures that roofing material manufacturers, building professionals, and testing laboratories follow globally recognized protocols for analyzing KEE-PVC roofing fabrics. The standard supports both process efficiency and product reliability through clear test procedures, defined safety requirements, and robust precision criteria, making it integral to the roofing and waterproofing industry’s quality assurance toolkit.

For official and current documentation, users are reminded to refer to the published version from ASTM International.

Standards Content (Sample)

This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: D8154 − 24
Standard Test Methods for
H-NMR Determination of Ketone-Ethylene-Ester and
Polyvinyl Chloride Contents in KEE-PVC Roofing Fabrics
This standard is issued under the fixed designation D8154; 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 (´) indicates an editorial change since the last revision or reapproval.
1. Scope E691 Practice for Conducting an Interlaboratory Study to
Determine the Precision of a Test Method
1.1 This test method pertains to the determination of the
relative contents of ketone-ethylene-ester (KEE) and polyvinyl
3. Terminology
chloride (PVC) after their extraction from reinforced roofing
3.1 Definitions—Terminology D1079 and Specification
membranes or fabrics. Based on proton nuclear magnetic
D6754/D6754M shall apply to this test method.
resonance spectroscopy ( H-NMR), the method allows for the
quantification of PVC with respect to an internal standard. The
4. Summary of Test Method
KEE content is then obtained by difference. The test method is
not applicable to membranes or blends that contain high
4.1 Test Methods—There are two related test methods to
molecular weight polymers other than PVC and KEE.
quantify PVC and KEE in roofing fabrics. In both methods, the
polymer blend is extracted from the fabric and purified by a
1.2 Units—The values stated in SI units are to be regarded
series of dissolution, centrifugation, and precipitation. After
as standard. No other units of measurement are included in this
drying, the blend is dissolved in deuterated tetrahydrofuran
standard.
along with a H-NMR internal standard. In Method A, PVC
1.3 This standard does not purport to address all of the
content is quantified by comparing its H-NMR signal with that
safety concerns, if any, associated with its use. It is the
of the internal standard, and KEE is obtained by difference.
responsibility of the user of this standard to establish appro-
Method B adds to Method A a calibration curve the slope of
priate safety, health, and environmental practices and deter-
which providing for a correction factor. This correction factor
mine the applicability of regulatory limitations prior to use.
is applied to the polymer content obtained by Method A to
1.4 This international standard was developed in accor-
provide for greater precision on the PVC and KEE contents.
dance with internationally recognized principles on standard-
ization established in the Decision on Principles for the
5. Significance and Use
Development of International Standards, Guides and Recom-
5.1 Determination of the percentage of KEE compound in
mendations issued by the World Trade Organization Technical
sheet roofing is of concern to many specifiers and building
Barriers to Trade (TBT) Committee.
owners. Method A, the faster method, is best used for quality
control. Method B may apply better to research and develop-
2. Referenced Documents
2 ment or investigative work.
2.1 ASTM Standards:
D1079 Terminology Relating to Roofing and Waterproofing
6. Interferences
D6754/D6754M Specification for Ketone Ethylene Ester
6.1 The NMR analysis of the polymer blend extracted from
Based Sheet Roofing
the sheet roofing is sensitive to impurities, including
E177 Practice for Use of the Terms Precision and Bias in
plasticizer, filler, reinforcement, and trace solvent (other than
ASTM Test Methods
the NMR solvent). The procedure here is meant to purify the
blend for proper analysis.
This test method is under the jurisdiction of ASTM Committee D08 on Roofing
and Waterproofing and is the direct responsibility of Subcommittee D08.18 on
7. Equipment and Apparatus
Nonbituminous Organic Roof Coverings.
Current edition approved Jan. 1, 2024. Published January 2024. Originally 7.1 Glassware. Erlenmeyer flask and stopper, 125 mL.
approved in 2017. Last previous edition approved in 2017 as D8154 – 17. DOI:
Weighing bottle, 25 mL.
10.1520/D8154-24.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or 7.2 Porcelain ware. Büchner funnel, 10 cm in diameter.
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
7.3 Platform shaker. Must accept 125 mL Erlenmeyer, and
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. allow for swirling at 120 to 150 rpm.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D8154 − 24
7.4 Metal spatula. To stir the suspension during the precipi- weights for safe operation. Refer to the operator’s manual for
tation step. details. Centrifugation flasks must be resistant to the fluid
being used and must not swell.
7.5 Pasteur pipettes. To transfer solubilized polymer and
solvent from one flask to another.
9.3 Magnetic Fields—NMR spectroscopy involves strong
magnetic fields. Analysis by NMR requires safety and equip-
7.6 Centrifuge. Capable of 10 000 RPM.
ment training. Follow local laboratory guidelines.
7.7 Centrifuge tubes. 50 mL. Must be resistant to THF, for
example, fluorinated ethylene propylene.
10. Sampling
7.8 Watch glass. To dry polymer in the oven.
10.1 Samples are obtained from sheet roofing or from
7.9 Vacuum oven. Adjustable to 65 6 2 °C.
pre-production runs. Cut two pieces of 4 cm taken 1 m apart
along the length of the same roll. Each piece will be analyzed
7.10 Vacuum pump. To provide for 100 kPa of vacuum in
for polymer content to provide for duplicate analysis.
the oven.
7.11 Balance. Sensitive to 0.000001 g (1 microgram).
11. Sample Preparation
7.12 NMR sample tubes. 5 mm in diameter.
11.1 Polymer Extraction and Purification Procedure:
7.13 NMR Fourier Transform Spectrometer. Equipped with
11.1.1 From each 4 cm piece of sheet, cut about 0.5 g into
a proton probe. 400 MHz field strength or higher is recom-
small pieces, approximately 3 mm by 3 mm. Place cut pieces
mended.
into a 125 mL Erlenmeyer flask and add 60 mL of hexane.
Stopper the flask and place it on a platform shaker to swirl at
8. Reagents and Materials
120 rpm for 24 h.
8.1 Water. 500 mL, and crushed ice, 1 kg, for an ice bath.
NOTE 1—Hexane is used to clean the sheet and extract low molecular
8.2 Whatman filter paper No. 2. For the Bückner funnel.
weight plasticizer that would affect the PVC and KEE contents measured
8.3 Lint-free paper towel. To blot sample dry of solvent. by NMR.
8.4 Hexane. Technical grade, 60 mL.
11.1.2 Filter off the hexane into a Büchner funnel with
cellulose Whatman filter paper No. 2. Place the pieces of
8.5 Tetrahydrofuran (THF). Technical grade, 150 mL.
sample onto a lint-free paper towel and blot them dry.
8.6 Methanol. Technical grade, 450 mL. Maintained near
11.1.3 Place sample pieces into a 125 mL Erlenmeyer flask,
5 °C in an ice bath.
add 45 mL of tetrahydrofuran (THF), and close the flask with
8.7 Deuterated tetrahydrofuran (THF-d8). 99.5 % pure or
its stopper. Place the flask on a platform shaker and stir its
better.
content at 150 rpm until sample polymer has completely
dissolved and there is no evidence of gel.
8.8 1,2,4,5-Tetrachloro-3-nitro-benzene. Certified reference
material, TCNB, 99.7 % pure or better.
NOTE 2—Dissolution time depends on composition. It may take up to
8.9 Polyvinyl chloride (PVC) powder. For calibration in 5 h for the sample to dissolve.
Method B. It is ideally obtained from the membrane producer.
11.1.4 Transfer dissolved sample to a 50 mL centrifugation
If this fails, PVC could be obtained from a primary source, that
tube. Rinse the Erlenmeyer flask with 5 mL of THF and use
is, a raw material producer, ascertaining that the product source
this rinse solvent to completely fill the centrifugation tube. Cap
and grade are the same as those used in actual sheet roofing
the tube and centrifuge its content for 30 min at 10 000 rpm.
production. PVC could be obtained for instance from oxyvi-
After centrifugation, carefully transfer the supernatant liquid
nyls. For best precision in polymer quantification, the raw
with a Pasteur pipette to a 125 mL Erlenmeyer flask (for
materials for calibration samples should be those used in the
transport and storage, if necessary), leaving the precipitated
membrane fabrication.
solid at the bottom of the centrifugation tube.
8.10 Ketone ethylene ester (KEE) pellets. For calibration in
11.1.5 Precipitate the dissolved polymer by pouring the
Method B. It is ideally obtained from the membrane producer.
supernatant THF into 150 mL of cold methanol (5 °C) in a
If this fails, KEE could be obtained from a primary source, that
400 mL beaker and stir with a metal spatula for 5 min. Allow
TM
is, DuPont (Elvaloy® polymer), ascertaining that the prod-
the mixture to stand for another 5 min at 5 °C (for example, in
uct grade is that used in the sheet roofing fabrication.
an ice bath) to allow for the polymer to precipitate out of
solution.
9. Hazards
11.1.6 Filter the polymer precipitate through a vacuum
9.1 Chemical Hazards—Several solvents are used in this
funnel over No. 2 Whatman filter paper. Remove the polymer
test method, including methanol, THF, hexane, along with
from the filter paper while it is still damp, and place the
TCNB. Check their material safety data sheet to identify
polymer onto a watch glass to dry the excess of THF in an oven
specific hazards. Follow local regulations for proper disposal
at 65 °C for 15 min.
of spent chemicals.
11.1.7 Repeat 11.1.3 – 11.1.6 twice for a total of three
9.2 Centrifugation—Centrifugation of dissolved sheet roof- iterations to retain a polymer sample free of interference as
ing involves high speeds and it must be balanced with counter defined in Section 6.
D8154 − 24
11.1.8 After three iterations as per 11.1.7, place the ex- processing as per 12.3, set to 100 the integral regions from 7.80
tracted and purified polymer sample into a 20 mL sample vial to 8.40 ppm for TCNB, and obtain the integration from 4.12 to
and dry it free of THF by heating it to 60 °C for 8 h under 4.75 ppm for PVC. Fig. X1.1 in Appendix X1 provides an
vacuum. example of a spectrum with integration.
NOTE 3—Thorough drying is required to remove traces of THF, which 12.3 Spectrum Processing—For quantitative NMR, the
will interfere with the calculated PVC-KEE content NMR analysis. THF
peaks must be as narrow and symmetric as possible and the
will be readily visible in the H-NMR spectrum. Before dissolution of the
integral line must reflect the surface area of spectral lines as
sample in deuterated-THF as per 11.2.1, the absence of protonated-THF
well as the absence of spectral lines (flat baseline). Note, for
may be verified by means of Fourier-transform infrared spectroscopy, or
instance, the flat baseline on the TCNB integration in Fig.
thermo-gravimetric analysis.
X1.1.
11.1.9 Reserve the polymer dried as per 11.1.8 in a flask to
12.3.1 Phasing—It is first necessary to greatly expand the
protect it from contaminant until it is used to prepare the NMR
vertical scale of the spectrum to see the base of the peaks and
sample.
make them as symmetric as possible by adjusting the phase so
11.2 Preparation of NMR Sample:
that the tails on each side of the peaks are as short and
11.2.1 Polymer Sample—Weigh in a small weighing pan
symmetric as possible. Phasing is done by adjusting two
and with a precision of 0.001 mg about 20 mg of TCNB and
parameters: the zero order and the first order phase and the
about 30 mg of polymer dried as per 11.1.8. Transfer these
process vary depending on the NMR software.
solids to a 5 mL weighting glass bottle. Use about 1 mL
...

This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
´1
Designation: D8154 − 17 D8154 − 24
Standard Test Methods for
H-NMR Determination of Ketone-Ethylene-Ester and
Polyvinyl Chloride Contents in KEE-PVC Roofing Fabrics
This standard is issued under the fixed designation D8154; 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 (´) indicates an editorial change since the last revision or reapproval.
ε NOTE—Editorially added Research Report information in April 2019.
1. Scope
1.1 This test method pertains to the determination of the relative contents of Ketone-Ethylene-Esterketone-ethylene-ester (KEE)
and Polyvinyl Chloridepolyvinyl chloride (PVC) after their extraction from reinforced roofing membranes,membranes or fabrics.
Based on Proton Nuclear Magnetic Resonance Spectroscopyproton nuclear magnetic resonance spectroscopy ( H-NMR), the
method allows for the quantification of PVC with respect to an internal standard. The KEE content is then obtained by difference.
The test method is not applicable to membranes or blends that contain high molecular weight polymers other than PVC and KEE.
1.2 Units—The values stated in SI units are to be regarded as standard. No other units of measurement are included in this
standard.
1.3 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety, health, and environmental practices and determine the applicability of
regulatory limitations prior to use.
1.4 This international standard was developed in accordance with internationally recognized principles on standardization
established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued
by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
2. Referenced Documents
2.1 ASTM Standards:
D1079 Terminology Relating to Roofing and Waterproofing
D6754/D6754M Specification for Ketone Ethylene Ester Based Sheet Roofing
E177 Practice for Use of the Terms Precision and Bias in ASTM Test Methods
E691 Practice for Conducting an Interlaboratory Study to Determine the Precision of a Test Method
3. Terminology
3.1 Definitions—Terminology D1079 and Specification D6754/D6754M shall apply to this test method.
This test method is under the jurisdiction of ASTM Committee D08 on Roofing and Waterproofing and is the direct responsibility of Subcommittee D08.18 on
Nonbituminous Organic Roof Coverings.
Current edition approved Nov. 1, 2017Jan. 1, 2024. Published November 2017January 2024. Originally approved in 2017. Last previous edition approved in 2017 as
D8154 – 17. DOI: 10.1520/D8154-17E01.10.1520/D8154-24.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D8154 − 24
4. Summary of Test Method
4.1 Test Methods—There are two related test methods to quantify PVC and KEE in roofing fabrics. In both methods, the polymer
blend is extracted from the fabric and purified by a series of dissolution, centrifugation, and precipitation. After drying, the blend
is dissolved in deuterated tetrahydrofuran along with a H-NMR internal standard. In Method A, PVC content is quantified by
comparing its H-NMR signal with that of the internal standard, and KEE is obtained by difference. Method B adds to Method
A a calibration curve the slope of which providing for a correction factor. This correction factor is applied to the polymer content
obtained by Method A to provide for greater precision on the PVC and KEE contents.
5. Significance and Use
5.1 Determination of the percentage of KEE compound in sheet roofing is of concern to many specifiers and building owners.
Method A, the faster method, is best used for quality control. Method B may apply better to research and development,development
or investigative work.
6. Interferences
6.1 The NMR analysis of the polymer blend extracted from the sheet roofing is sensitive to impurities, including plasticizer, filler,
reinforcement, and trace solvent (other than the NMR solvent). The procedure here is meant to purify the blend for proper analysis.
7. Equipment and Apparatus
7.1 Glassware. Erlenmeyer flask and stopper, 125 mL. Weighing bottle, 25 mL.
7.2 Porcelain ware. Büchner funnel, 10 cm in diameter.
7.3 Platform shaker. Must accept 125 mL Erlenmeyer, and allow for swirling at 120 to 150 rpm.
7.4 Metal spatula. To stir the suspension during the precipitation step.
7.5 Pasteur pipettes. To transfer solubilized polymer and solvent from one flask to another.
7.6 Centrifuge. Capable of 10 000 RPM.
7.7 Centrifuge tubes. 50 mL. Must be resistant to THF, for example, Fluorinated Ethylene Propylene.fluorinated ethylene
propylene.
7.8 Watch-glass. Watch glass. To dry polymer in the oven.
7.9 Vacuum Oven.oven. Adjustable to 65 6 2°C.2 °C.
7.10 Vacuum pump. To provide for 100 kPa of vacuum in the oven.
7.11 Balance. Sensitive to 0.000001 g (1 microgram).
7.12 NMR sample tubes. 5 mm in diameter.
7.13 NMR Fourier Transform Spectrometer. Equipped with a proton probe. 400 MHz field strength or higher is recommended.
8. Reagents and Materials
8.1 Water. 500 mL, and crushed ice, 1 kg, for an ice bath.
8.2 Whatman filter paper No. 2. For the Bückner funnel.
D8154 − 24
8.3 Lint-free paper towel. To blot sample dry of solvent.
8.4 Hexane. Technical grade, 60 mL.
8.5 Tetrahydrofuran (THF). Technical grade, 150 mL.
8.6 Methanol. Technical grade, 450 mL. Maintained near 5°C5 °C in an ice bath.
8.7 Deuterated tetrahydrofuran (THF-d8). 99.5 % pure or better.
8.8 1,2,4,5–Tetrachloro-3-nitro-benzene.1,2,4,5-Tetrachloro-3-nitro-benzene. Certified reference material, TCNB, 99.7 % pure or
better.
8.9 Polyvinyl chloride (PVC) powder. For calibration in Method B. It is ideally obtained from the membrane producer. If this fails,
PVC could be obtained from a primary source, that is, a raw material producer, ascertaining that the product source and grade isare
the same as thatthose used in actual sheet roofing production. PVC could be obtained for instance from OxyVinyls.oxyvinyls. For
best precision in polymer quantification, the raw materials for calibration samples should be those used in the membrane
fabrication.
8.10 Ketone ethylene ester (KEE) pellets. For calibration in Method B. It is ideally obtained from the membrane producer. If this
TM
fails, KEE could be obtained from a primary source, that is, DuPont (Elvaloy® polymer), ascertaining that the product grade
is that used in the sheet roofing fabrication.
9. Hazards
9.1 Chemical Hazards—Several solvents are used in this test method, including methanol, THF, hexane, along with TCNB. Check
their material safety datasheet data sheet to identify specific hazards. Follow local regulations for proper disposal of spent
chemicals.
9.2 Centrifugation—Centrifugation of dissolved sheet roofing involves high speeds and it must be balanced with counter weights
for safe operation. Refer to the operator’s manual for details. Centrifugation flasks must be resistant to the fluid being used and
must not swell.
9.3 Magnetic Fields—NMR spectroscopy involves strong magnetic fields. Analysis by NMR requires safety and equipment
training. Follow local laboratory guidelines.
10. Sampling
10.1 Samples are obtained from sheet roofing,roofing or from pre-production runs. Cut two pieces of 4 cm taken 1 m apart along
the length of the same roll. Each piece will be analyzed for polymer content to provide for duplicate analysis.
11. Sample Preparation
11.1 Polymer Extraction and Purification Procedure:
11.1.1 From each 4 cm piece of sheet, cut about 0.5 g into small pieces, approximately 3 mm ×by 3 mm. Place cut pieces into
a 125 mL Erlenmeyer flask and add 60 mL of hexane. Stopper the flask and place it on a platform shaker to swirl at 120 rpm for
24 hours.24 h.
NOTE 1—Hexane is used to clean the sheet and extract low molecular weight plasticizer that would affect the PVC and KEE contents measured by NMR.
11.1.2 Filter off the hexane into a Büchner funnel with cellulose Whatman filter paper No-2. No. 2. Place the pieces of sample
onto a lint free lint-free paper towel and blot them dry.
D8154 − 24
11.1.3 Place sample pieces into a 125 mL Erlenmeyer flask, add 45 mL of tetrahydrofuran (THF)(THF), and close the flask with
its stopper. Place the flask on a platform shaker and stir its content at 150 rpm until sample polymer has completely dissolved and
there is no evidence of gel.
NOTE 2—Dissolution time depends on composition. It may take up to 5 hours 5 h for the sample to dissolve.
11.1.4 Transfer dissolved sample to a 50 mL centrifugation tube. Rinse the Erlenmeyer flask with 5 mL of THF and use this rinse
solvent to completely fill the centrifugation tube. Cap the tube and centrifuge its content for 30 minutesmin at 10 000 rpm. After
centrifugation, carefully transfer the supernatant liquid with a Pasteur pipette to a 125 mL Erlenmeyer flask (for transport and
storage, if necessary), leaving the precipitated solid at the bottom of the centrifugation tube.
11.1.5 Precipitate the dissolved polymer by pouring the supernatant THF into 150 mL of cold methanol (5°C)(5 °C) in a 400 mL
400 mL beaker and stir with a metal spatula for 5 minutes.min. Allow the mixture to stand for another 5 min at 5°C5 °C (for
example, in an ice bath) to allow for the polymer to precipitate out of solution.
11.1.6 Filter the polymer precipitate through a vacuum funnel over No. 2 Whatman filter paper. Remove the polymer from the
filter paper while it is still damp, and place the polymer onto a watch-glass watch glass to dry the excess of THF in an oven at
65°C65 °C for 15 minutes.min.
11.1.7 Repeat 11.1.3 – 11.1.6 twice for a total of three iterations to retain a polymer sample free of interference as defined in
Section 6.
11.1.8 After three iterations as per 11.1.7, place the extracted and purified polymer sample into a 20 mL sample vial and dry it
free of THF by heating it to 60°C for 8 hours 60 °C for 8 h under vacuum.
NOTE 3—Thorough drying is required to remove traces of THF, which will interfere with the calculated PVC-KEE content NMR analysis. THF will be
readily visible in the H-NMR spectrum. Before dissolution of the sample in deuterated-THF as per 11.2.1, the absence of protonated-THF may be verified
by means of Fourier-transform infrared spectroscopy, or thermo-gravimetric analysis.
11.1.9 Reserve the polymer dried as per 11.1.8 in a flask to protect it from contaminant until it is used to prepare the NMR sample.
11.2 Preparation of NMR Sample:
11.2.1 Polymer Sample—Weigh in a small weighing pan and with a precision of 0.001 mg about 20 mg of TCNB and about 30
mg of polymer dried as per 11.1.8. Transfer these solids to a 5 mL weighting glass bottle. Use about 1 mL of THF-d to wash
residual solid in the weighting pan and pipet it out to the glass bottle. Close the weighing glass bottle with its lid, and leave the
polymer-TCNB solid mixture to dissolve overnight. With a pipette, transfer the solution into a 5 mm NMR tube.
NOTE 4—Keep aside the weights of TCNB and the dried polymer for use in the calculation of PVC and KEE content in Section 13.
11.2.2 Calibration Samples—Calibration samples have PVC/KEE weight ratios close to 20/80, 30/70, 40/60, 50/50, and 60/40.
Samples are prepared by individually weightingweighing between about 5 mg to 25 mg of PVC and KEE for a total polymer
content near 30 mg. Weigh in a small weighing pan and with a precision of 0.001 mg about 20 mg of TCNB and about 30 mg
of the PVC/KEE mixture with a set ratio. Transfer these solids to a 5 mL weightingweighing glass bottle. Use about 1 mL of
THF-d to wash residual solid in the weightingweighing pan and pipet it out to the weighing bottle. Close the weighing bottle with
its lid, and leave the polymer-TCNB solid mixture to dissolve overnight. With a pipette, transfer the solution into a 5 mm NMR
tube. Table X1.1 in Appendix X1 provides an example of calibration sample compositions.
NOTE 5—Keep aside the weights of TCNB, PVC, and KEE for use in the calibration curve and calculation of PVC and KEE as per 13.1.2.
12. NMR Analysis
12.1 Acquisition Parameters—The proton-NMR probe temperature is to be set to 30°C30 °C and sample is to be left to stabilize
for 20 minutesmin in the probe prior to testing. Measure spin-lattice relaxation, T , by inversion recovery. Set the relaxation delay
to about six times the value of T to ascertain that full relaxation is achieved in the quantitative experiment. For instance, a 60 s
relaxation delay is used for a T of 9.9 s.
D8154 − 24
NOTE 6—Probe tuning and 90 deg
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