ASTM D914-00(2006)
(Test Method)Standard Test Methods for Ethylcellulose
Standard Test Methods for Ethylcellulose
SIGNIFICANCE AND USE
The results of this test are used for calculating the total solids in the sample and, by common usage, all materials volatile at this test temperature are designated as moisture.
Moisture analysis (along with sulfated ash) is used to calculate the amount of active polymer in the material and shall be considered when determining the amount of ethylcellulose in various functions.
SCOPE
1.1 These test methods cover the testing of ethylcellulose.
1.2 The test procedures appear in the following order: SectionsMoisture to Sulfated Ash to Chlorides (as Sodium Chloride) to Ethoxyl Content to Viscosity to
1.3The values stated in SI units are to be regarded as the standard. The values given in parentheses are for information only.
This standard may involve hazardous materials, operations, and equipment. 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 and health practices and determine the applicability of regulatory limitations prior to use.
1.4 This test method covers the determination of the volatile content of ethylcellulose.
General Information
Relations
Standards Content (Sample)
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: D914 − 00 (Reapproved 2006)
StandardTest Methods for
Ethylcellulose
This standard is issued under the fixed designation D914; 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.
This standard has been approved for use by agencies of the Department of Defense.
1. Scope conform to the specifications of the Committee on Analytical
Reagents of the American Chemical Society, where such
1.1 These test methods cover the testing of ethylcellulose.
specifications are available. Where such specifications have
1.2 The test procedures appear in the following order:
not been established, reagents of the best grade available shall
Sections
be used. References to water shall be understood to mean
Moisture 4 to 6
distilled water.
Sulfated Ash 7 to 11
Chlorides (as Sodium Chloride) 12 to 16
Ethoxyl Content 20 to 24 MOISTURE
Viscosity 25 to 39
1.3 The values stated in SI units are to be regarded as
4. Scope
standard. The values given in parentheses are for information
4.1 Thistestmethodcoversthedeterminationofthevolatile
only.
content of ethylcellulose.
1.4 This standard may involve hazardous materials,
operations, and equipment. This standard does not purport to
5. Significance and Use
address all of the safety concerns, if any, associated with its
5.1 The results of this test are used for calculating the total
use. It is the responsibility of the user of this standard to
solids in the sample and, by common usage, all materials
establish appropriate safety and health practices and deter-
volatile at this test temperature are designated as moisture.
mine the applicability of regulatory limitations prior to use.
5.2 Moisture analysis (along with sulfated ash) is used to
2. Referenced Documents
calculatetheamountofactivepolymerinthematerialandshall
2.1 ASTM Standards:
be considered when determining the amount of ethylcellulose
D362 Specification for Industrial Grade Toluene
in various functions.
D446 Specifications and Operating Instructions for Glass
Capillary Kinematic Viscometers
6. Apparatus
D841 Specification for Nitration Grade Toluene
6.1 Oven, gravity convection, capable of maintaining a
D4794 Test Method for Determination of Ethoxyl or Hy-
temperature of 105 6 3°C.
droxyethoxyl Substitution in Cellulose Ether Products by
Gas Chromatography
6.2 Weighing Bottles.
E1 Specification for ASTM Liquid-in-Glass Thermometers
6.3 Analytical Balance.
3. Purity of Reagents and Materials
7. Procedure
3.1 Reagent grade chemicals shall be used in all tests.
Unless otherwise indicated, all of the reagents used shall
7.1 Weigh accurately 2 to5gofthe sample to the nearest
0.001 g into a tared dish (fitted with a lid) and dry for2hinan
These test methods are under the jurisdiction of ASTM Committee D01 on
oven at 100 to 105°C. Remove the dish from the oven, cover
Paint and Related Coatings, Materials, and Applications and are the direct
with a lid, cool in a desiccator, and weigh.
responsibility of Subcommittee D01.36 on Cellulose and Cellulose Derivatives.
Current edition approved April 1, 2006. Published April 2006. Originally
approved in 1947. Last previous edition approved in 2000 as D914 – 00. DOI:
10.1520/D0914-00R06.
2 4
For referenced ASTM standards, visit the ASTM website, www.astm.org, or Reagent Chemicals, American Chemical Society Specifications, American
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Standards volume information, refer to the standard’s Document Summary page on listed by the American Chemical Society, see Analar Standards for Laboratory
the ASTM website. Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
Withdrawn. The last approved version of this historical standard is referenced and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
on www.astm.org. MD.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D914 − 00 (Reapproved 2006)
8. Calculation 16. Precision and Bias
8.1 Calculate the percent moisture, M as follows: 16.1 Precision—Statistical analysis of interlaboratory (re-
producibility) test results indicates a precision of 610 % at the
M 5 A/B 3100 (1)
~ !
95 % confidence level.
where:
16.2 Bias—No statement of bias can be made as no suitable
A = mass loss on heating, g, and
reference material is available as a standard.
B = sample used, g.
CHLORIDES (as Sodium Chloride)
9. Precision and Bias
17. Scope
9.1 Precision—Statistical analysis of intralaboratory (re-
peatability) test results indicates a precision of 65 % at the
17.1 This test method covers the determination of the
95 % confidence level.
chloride content of ethylcellulose.
9.2 Bias—No statement of bias can be made as no suitable
18. Significance and Use
reference material is available as a standard.
18.1 Sodium chloride is a major by-product of the ethylcel-
SULFATED ASH
lulose manufacturing process. This test is a measure of the
purity of ethylcellulose. Chlorides may also affect solution
10. Scope
properties.
10.1 This test method covers the determination of the
residue on ignition of ethylcellulose after a specimen has been
19. Apparatus
treated with sulfuric acid.
19.1 Titration pH Meter.
11. Significance and Use
19.2 Mercury-Mercurous Sulfate Reference Electrode—The
11.1 This test method (along with moisture) is used to electrode uses a potassium sulfate electrolyte to avoid chloride
contamination from a chloride electrolyte.
calculate the active polymer in the material. It shall be used
when testing ethylcellulose in United States government regu-
19.3 Silver-Silver Chloride Electrode—The electrode is
lated applications. Excessive ash may also affect solution
coated with silver chloride periodically. Prepare the electrode
clarity and film properties.
by polishing with fine steel wool, briefly soaking it in 5 %
potassium cyanide solution, and rinsing it with water. Coat the
12. Apparatus
electrode with silver chloride by electrodeposition from 0.1 N
12.1 Muffle Furnace.
potassiumchloridesolutionusinga3-Vdrycellandaplatinum
wire electrode. Connect the silver electrode to the positive pole
12.2 Crucibles, either porcelain, 30–mLhigh, form cracked,
of the battery and electrolyze for 20 s; then reverse the
platinum.
connections for 5 s. Repeat these operations twice, and finally,
13. Reagent
chloridize the silver electrode for 20 s at the positive terminal.
Store the silver electrode in 0.1 N potassium chloride solution.
13.1 Sulfuric Acid (sp gr 1.84)—Concentrated sulfuric acid
Rinse the electrode with water and wipe it with a soft tissue
(H SO ).
2 4
before each titration.
14. Procedure
19.4 Salt Bridge for Reference Electrode—Fig. 1 shows one
14.1 Ignite a crucible for 10 to 15 min at 800 6 25°C, cool
configuration in use. Exact dimensions are not important. The
in a desiccator, and weigh to the nearest 0.001 g.
salt bridge is used to keep the reference electrode from
plugging with the ethylcellulose slurry.
14.2 Weigh about5gof sample to the nearest 0.001 g
(previously dried for3hat 105°C) into the crucible. Burn off
19.5 Air-Driven Stirrer.
the bulk of the carbonaceous material directly over a flame.
After cooling, add 1 mLof H SO in such a way as to moisten 20. Reagents
2 4
the entire ash; then cautiously heat with the burner to dense
20.1 Ethanol (95 volume %), undenatured or specially
white fumes. Ignite in a muffle furnace at 800 6 25°C until all
denatured conforming to Formula 2B of the U.S. Bureau of
signs of carbon are gone. Cool in a desiccator and reweigh to
Internal Revenue.
the nearest 0.001 g.
20.2 Ethanol-Distilled Water Solvent Mixture (80 + 20)—
15. Calculation Mix 800 g of 2B ethanol with 200 g of water. Add 7.5 g of
aerosol OT 100 % surface-active agent per 3000 g of ethanol-
15.1 Calculate the percent ash (as sulfate), C, as follows:
water mixture.
C 5 ~A/B! 3100 (2)
20.3 Potassium Nitrate (KNO ) Solution (saturated) for salt
where:
bridge (Fig. 1).
A = ash, g, and
20.4 Silver Nitrate, Standard Solution (0.02 N)—Dissolve
B = sample used, g.
3.4 g of silver nitrate (AgNO ) in water, dilute to 1 L with
D914 − 00 (Reapproved 2006)
mL of H SO (1 + 16) and agitate for 3 to 4 min to allow the
2 4
system to reach equilibrium.
21.3 Titrate slowly with the 0.02 N AgNO solution. Make
intermittent additions of 0.1 mL. It is advisable to allow longer
periods of time between additions of titrant as the end point is
approached to avoid passing the equivalence point. Run a
blank by the same procedure.
22. Calculation
22.1 Calculate parts per million of chlorides as NaCl, C,as
follows:
C 5 VN 30.05845 /W 31 000 000 (4)
@~ ! #
where:
V = AgNO solution, mL,
N = normality of AgNO solution,
W = sample used, g, and
0.05845 = milliequivalent mass of NaCl.
23. Precision and Bias
1 1 5 3 1 7 1 23.1 Precision—Statistical analysis of interlaboratory (re-
in. ⁄32 ⁄8 ⁄16 ⁄8 ⁄2 ⁄8 1 ⁄2 3 6
mm 0.8 3.2 7.9 9.5 12.7 22.2 38 76 152
producibility) test results indicates a precision of 65 % at the
95 % confidence level.
FIG. 1 Salt Bridge and Reference Electrode for Chloride Determi-
23.2 Bias—No statement of bias can be made as no suitable
nation
reference material is available as a standard.
ETHOXYL CONTENT
24. Scope
waterinavolumetricflask,andmix.Weighexactly0.5845gof
dry, primary standard sodium chloride (NaCl), dissolve in 25
24.1 This test method covers the determination of the
mLof water, and dilute to 1 Lwith water in a volumetric flask.
ethoxyl content of ethylcellulose.
Add 10 mL of H SO (1 + 16) to each aliquot before titrating.
2 4
24.2 For an alternative method see Test Method D4794.
Titrate aliquots of this solution potentiometrically with the
AgNO solution. Calculate the normality, N, of the AgNO
3 3
25. Significance and Use
solution as follows:
25.1 This test method determines the amount of substituent
N 5 ~A/B! 30.01 (3)
groups added to the cellulose backbone. The level can greatly
affect solution properties, rheology, solubility parameters, and
where:
film properties.
A = 0.01 N NaCl solution added, mL, and
B = AgNO solution required for the titration, mL.
26. Apparatus
20.5 Sulfuric Acid (1 + 16) —Add 1 volume of concentrated
26.1 Distillation Apparatus, as illustrated in Fig. 2, consist-
sulfuric acid (H SO , sp gr 1.84) slowly with stirring into 16
2 4
ing of a boiling flask with a side arm for admission of carbon
volumes of water.
dioxide (CO ) or nitrogen, an air condenser with a trap, and a
20.6 Toluene, meeting the requirements of Specification
receiver.
D362.
26.2 Oil Bath, equipped with a heating device, preferably
20.7 Toluene-Ethanol Solvent Mixture (90 + 10)—Mix 900
electrical, so that the bath can be maintained at 145 to 150°C.
g of toluene with 100 g of ethanol.
27. Reagents
21. Procedure
27.1 Bromine Solution—Dissolve 5 mL of bromine in 145
21.1 Weigh accurately 10 g of sample to the nearest 0.001 g mL of the potassium acetate (KC H O ) solution. Prepare the
2 3 2
(previously dried for2hat100to 105°C) and transfer to a bromine solution fresh daily in a hood to remove bromine
600-mL beaker containing 200 mL of the toluene-ethanol vapors.
solvent mixture. Stir with an air-driven stirrer until solution is
27.2 Carbon Dioxide—Pass the CO through a bubble
complete.
counter and a dry trap, and then through a pressure regulator
21.2 Add 200 mL of the ethanol-water mixture and agitate consisting of a glass tee whose vertical arm extends almost to
for 5 min to form a uniform emulsion. Immerse the electrodes the bottom of a 254-mm (10-in.) column of water. A screw
in the emulsion using an air-driven stirrer for mixing. Add 10 clamp shall be attached to the thin-walled rubber tubing
D914 − 00 (Reapproved 2006)
keepthecurrentofCO goingafterthedistillationisendedand
until the apparatus has cooled; this will prevent air from being
sucked into the apparatus. Put the purified HI in small, brown,
glass-stoppered bottles, previously swept out with CO , and
seal the stoppers with molten paraffin. Store in a dark place.To
minimize decomposition of HI due to contact with air, run CO
into the bottle while withdrawing portions of the acid for use.
27.6 PhosphorusSlurry(0.06g/100mL)—Addabout0.06g
ofredphosphorusto100mLofwater.Shakewellbeforeusing.
27.7 Potassium Acetate Solution (100 g/L)—Dissolve 100 g
of anhydrous potassium acetate (KC H O ) crystal in 1 L of a
2 3 2
solution containing 900 mL of glacial acetic acid and 100 mL
of acetic anhydride.
27.8 Potassium Iodide (KI).
27.9 Sodium Acetate Solution (220 g/L)—Dissolve 220 g of
anhydrous sodium acetate in water and dilute to 1 L.
27.10 Sodium Thiosulfate, Standard Solution (0.1 N)—
Dissolve 25 g of sodium thiosulfate (Na S O ·5H O) in 200
2 2 3 2
mL of water and dilute to 1 L. Use freshly boiled and cooled
water. It is preferable to allow the solution to stand for a few
days before standardization. Standardize the solution against
0.1000 N potassium dichromate (K Cr O ) solution prepared
2 2 7
by dissolving exactly 4.9037 g of K Cr O (National Institute
2 2 7
of Standards and Technology Standard Sample No. 136) in
water and diluting to 1 L in a volumetric flask. By means of a
buret, measure accurately 35 to 45 mLof the K Cr O solution
2 2 7
into a 250-mL Erlenmeyer flask. Add2gofKIand50mLof
FIG. 2 Distillation Apparatus for Ethoxyl Determination
sulfuricacid(H SO ,1 + 9)andallowtostandforabout5min.
2 4
Titrate the liberated iodine with the Na S O solution, using
2 2 3
starch indicator solution near the end point. At the end point,
connecting the horizontal arm of the tee with the boiling flask.
This arrangement permits regulation of the flow of gas and the blue color of the starch indicator will be destroyed, leaving
the pale green color of the chromate ion. The normality of the
allowsanyexcessgastoescape.Nitrogenmaybeusedinplace
Na S O , solution should be checked at least once a week.
of CO .
2 2 3
Calculate the normality, N, of the Na S O solution as follows:
2 2 3
27.3 Formic Acid (90 %).
N 5 A/B 30.1 (5)
~ !
27.4 Gelatin Capsules—Gelatin capsules of a suitable size
to hold from 50 to 60 mg of the dried sample will be required. where:
A = 0.1000 N K Cr O solution added, mL, and
27.5 Hydriodic Acid (sp gr 1.70) —Hydriodic acid (HI)
2 2 7
B =Na S O solution required for the titration, mL.
forms with water a constant-boiling mixture (boiling point 126 2 2 3
to127°C)thatc
...
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