ASTM D817-96

Standard Test Methods of Testing Cellulose Acetate Propionate and Cellulose Acetate Butyrate

SCOPE
1.1 These test methods cover procedures for the testing of cellulose acetate propionates and acetate butyrates. These esters may vary widely in composition and properties, so certain of the procedures can be used only in the ranges of composition where they are suitable.  
1.2 The test procedures appear in the following sections:  Sections Acetyl Propionyl or Butyryl Contents 28 to 37 Acetyl Content, Apparent 18 to 27 Acidity Free 12 to 17 Ash 7 to 10 Color and Haze 77 to 81 Heat Stability 57 to 65 Hydroxyl Content 38 to 44 Hydroxyl Content, Primary 46 to 50 Intrinsic Viscosity 67 to 71 Moisture Content 5 to 6 Sulfur or Sulfate Content 51 to 56 Viscosity 74 to 75 Limiting Viscosity Number 67 to 71
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 and health practices and determine the applicability of regulatory limitations prior to use.

General Information

• Status: Historical
• Publication Date: 31-Dec-1995
• ICS: 85.040 - Pulps
• Technical Committee: D01 - Paint and Related Coatings, Materials, and Applications
• Drafting Committee: D01.36 - Cellulose and Cellulose Derivatives

Relations

• Replaced By: ASTM D817-96(2004) - Standard Test Methods of Testing Cellulose Acetate Propionate and Cellulose Acetate Butyrate
• Effective Date: 01-Jun-2004
• Referred By: ASTM D1343-95(2019) - Standard Test Method for Viscosity of Cellulose Derivatives by Ball-Drop Method
• Effective Date: 01-Jan-1996
• Referred By: ASTM E1899-23 - Standard Test Method for Hydroxyl Groups Using Reaction with <emph type="ital">p</emph >-Toluenesulfonyl Isocyanate (TSI) and Potentiometric Titration with Tetrabutylammonium Hydroxide
• Effective Date: 01-Jan-1996
• Referred By: ASTM D5897-13(2021) - Standard Test Method for Determination of Percent Hydroxyl on Cellulose Esters by Potentiometric Titration—Alternative Method
• Effective Date: 01-Jan-1996
• Referred By: ASTM D2929-89(2019)e1 - Standard Test Method for Sulfur Content of Cellulosic Materials by X-Ray Fluorescence
• Effective Date: 01-Jan-1996

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NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.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: D 817 – 96
Standard Test Methods of Testing
Cellulose Acetate Propionate and Cellulose Acetate
Butyrate
This standard is issued under the fixed designation D 817; 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.
1. Scope 3. Reagents
1.1 These test methods cover procedures for the testing of 3.1 Purity of Reagents—Reagent grade chemicals shall be
cellulose acetate propionates and acetate butyrates. These used in all tests. Unless otherwise indicated, it is intended that
esters may vary widely in composition and properties, so all reagents shall conform to the specifications of the Commit-
certain of the procedures can be used only in the ranges of tee on Analytical Reagents of the American Chemical Society,
composition where they are suitable. where such specifications are available. Other grades may be
1.2 The test procedures appear in the following sections: used, provided it is first ascertained that the reagent is of
sufficiently high purity to permit its use without lessening the
Sections
Acetyl Propionyl or Butyryl Contents 28-37
accuracy of the determination.
Acetyl Content, Apparent 18-27
Acidity, Free 12-17
4. Conditioning
Ash 7-10
Color and Haze 77-81
4.1 Conditioning—Condition the test specimens at 23 6
Heat Stability 57-65
2°C (73.4 6 3.6°F) and 50 6 5 percent relative humidity for
Hydroxyl Content 38-44
not less than 40 h prior to test in accordance with Procedure A
Hydroxyl Content, Primary 46-50
Intrinsic Viscosity 67-71
of Methods D 618, for those tests where conditioning is
Moisture Content 5-6
required. In cases of disagreement, the tolerances shall be6
Sulfur or Sulfate Content 51-56
1°C (61.8°F) and 62 percent relative humidity.
Viscosity 74-75
Limiting Viscosity Number 67-71
4.2 Test Conditions—Conduct tests in the Standard Labora-
tory Atmosphere of 23 6 2°C (73.4 6 3.6°F) and 50 6 5%
1.3 This standard does not purport to address the safety
relative humidity, unless otherwise specified in the test meth-
concerns, if any, associated with its use. It is the responsibility
ods. In cases of disagreements, the tolerances shall be 61°C
of the user of this standard to establish appropriate safety and
(61.8°F) and6 2 % relative humidity.
health practices and determine the applicability of regulatory
limitations prior to use.
MOISTURE CONTENT
2. Referenced Documents
5. Procedure
2.1 ASTM Standards:
5.1 Transfer about5gofthe sample to a tared, low,
D 618 Practice for Conditioning Plastics and Electrical
wide-form weighing bottle and weigh to the nearest 0.001 g.
Insulating Materials for Testing
Dry in an oven for2hat105 6 3°C. Remove the bottle from
D 1343 Test Method for Viscosity of Cellulose Derivatives
the oven, cover, cool in a desiccator, and weigh.
by Ball-Drop Method
D 2929 Test Method for Sulfur Content of Cellulosic Ma-
6. Calculation
terials by X-Ray Fluorescence
6.1 Calculate the percentage of moisture as follows:
D 5897 Test Method for Determination of Percent Hydroxyl
Moisture, % 5 ~A/B! 3 100 (1)
on Cellulose Esters by Potentiometric Titration—
Alternative Method
where:
These test methods are under the jurisdiction of ASTM Committee D-1 on Paint
and Related Coatings, Materials, and Applications and are the direct responsibility Reagent Chemicals, American Chemical Society Specifications, American
of Subcommittee D01.36 on Cellulose and Cellulose Derivatives. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Current edition approved Nov. 10, 1996. Published January 1997. Originally listed by the American Chemical Society, see Analar Standards for Laboratory
published as D 817 – 44 T. Last previous edition D 817 – 91. Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
Annual Book of ASTM Standards, Vol 08.01. and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
Annual Book of ASTM Standards, Vol 06.03. MD.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D 817
Test Method A—For Samples Containing Not More than
A 5 weight loss on heating, g, and
About 30 % Propionyl or Butyryl
B 5 sample used, g.
13. Procedure
ASH
13.1 Shake5gofthe sample, corrected for moisture content
7. Significance and Use
if necessary, in a 250-mL Erlenmeyer flask with 150 mL of
7.1 Ash content gives an estimate of the inorganic content
freshly boiled, cold water. Stopper the flask and allow it to
of cellulose ester samples. The presence of high levels of
stand for 3 h. Filter off the cellulose ester and wash it with
inorganic content (ash) can be detrimental to the melt stability
water. Titrate the combined filtrate and washings with 0.01 N
and optical clarity of a cellulose ester in melt processing or act
NaOH solution, using phenolphthalein indicator solution.
as a potential source of insolubles when the ester is used in
13.2 Run a blank determination on the water, using the same
solution.
volume as was used in extracting the sample.
8. Procedure
14. Calculation
8.1 Dry the sample for2hat105 6 3°C and weigh 10 to 50
14.1 Calculate the percentage of acidity as free acetic acid
g, to the nearest 0.01 to 0.1 g, depending on its ash content and
as follows:
the accuracy desired. Burn directly over a flame in a 100-mL
Free acetic acid, % 5 A 2 B!C 3 0.06 /W 3 100 (3)
$@~ # %
tared platinum crucible that has been heated to constant weight
and weighed to the nearest 0.1 mg. Add the sample in portions
where:
if more than 10 g is taken. The sample should burn gently and A 5 NaOH solution used to titrate the sample, mL,
the portions should be added as the flame subsides. Continue B 5 NaOH solution used to titrate the blank, mL,
heating with a burner only as long as the residue burns with a C 5 normality of the NaOH solution, and
W 5 sample used, g.
flame. Transfer the crucible to a muffle furnace and heat at 550
to 600°C for 3 h, or longer if required, to burn all the carbon.
Test Method B—For Samples Containing More than About
Allow the crucible to cool and then transfer it, while still warm,
7 % Propionyl or Butyryl and Particularly Suitable for
to a desiccator. When the crucible has cooled to room tem-
Samples Containing More than 30 % Propionyl or Butyryl
perature, weigh accurately to the nearest 0.1 mg.
15. Procedure
9. Calculation
15.1 Dissolve 10.0 g of the sample, corrected for moisture
9.1 Calculate the percentage of ash as follows:
content if necessary, in 200 mL of neutral acetone plus 20 mL
Ash, % 5 ~A/B! 3 100 (2)
of water. When completely dissolved, add 50 mL of water and
shake well to precipitate the ester in a finely divided form. Add
where:
3 drops of methyl red indicator solution and titrate to a
A 5 ash, g, and
lemon-yellow end point and 0.01 N NaOH solution.
B 5 sample used, g.
15.2 Make a blank determination on the reagents.
10. Precision and Bias
16. Calculation
10.1 No statement on bias can be made as no reference
16.1 Calculate the free acid content as acetic acid as
material is available as a standard.
directed in Section 14.
FREE ACIDITY
17. Precision and Bias
11. Significance and Use
17.1 No statement on bias can be made as no reference
11.1 Free acidity is a measure of unesterified organic acid in
material is available as a standard.
the ester. The presence of high levels of free acid is potentially
detrimental to melt processing of the ester and can impact the APPARENT ACETYL CONTENT
odor of the ester.
18. Scope
12. Reagents
18.1 The test methods described in the following 20 to 26
12.1 Acetone, neutral. cover the determination of the saponification value of the
12.2 Methyl Red Indicator Solution (0.4 g/L)—Dissolve 0.1 sample calculated as percentage of apparent acetyl, equivalent
g of methyl red in 3.72 mL of 0.1000 N NaOH solution and weight 43. This value is required in the calculation of acetyl
dilute to 250 mL with water. Filter if necessary. and propionyl or butyryl contents in 36.1.
12.3 Phenolphthalein Indicator Solution (1 g/100 mL)— 18.2 The test method used should be specified or agreed
Dissolve 1 g phenolphthalein in 100 mL of ethyl alco- upon. The choice depends on the propionyl or butyryl content
hol (95 % ). and the physical condition of the sample. Ordinarily, Test
12.4 Sodium Hydroxide, Standard Solution (0.01 N)— Method A is recommended for samples having less than about
Prepare and standardize a 0.01 N solution of sodium hydroxide 35 % propionyl or butyryl and Test Method B for samples
(NaOH). having more than that amount.
D 817
NOTE 1—Potassium acid phthalate is used so that the concentration of
19. Significance and Use
the NaOH in contact with the solvent in the blank will be approximately
19.1 Apparent acetyl content is a measure of the saponifi-
the same as that in contact with the sample and so that the titration of the
cation value of the ester. Apparent acetyl value is required in
blank will be approximately the same as the titration of the sample, thus
the calculation of acetyl, propionyl, and butyryl content in
avoiding errors caused by using a different buret for the titration of the
36.1. blank and the sample or by refilling the 15-mL buret. If desired, however,
the potassium acid phthalate may be omitted.
Test Method A—For Samples Containing Less than About
22.2 For acetone-soluble sample, put the sample into solu-
35 % Propionyl or Butyryl
tion as follows: Add 150 mL of acetone and 5 to 10 mL of
water and swirl to mix. Stopper the flask and allow it to stand
20. Apparatus
with occasional swirling until solution is complete. Solution
20.1 Weighing Bottle, glass-stoppered, 15-mL capacity,
may be hastened by magnetic stirring or by any suitable
25-mm diameter by 50 mm high.
mechanical shaking that will provide a gentle rocking type of
20.2 Tray, copper or aluminum, approximately 137 mm
agitation to avoid splashing the solution on the stopper. It is
square, containing 25 compartments 25 mm square. Each
essential that complete solution be effected.
compartment shall have the correct dimensions to contain one
22.3 For acetone-insoluble samples of low propionyl or
weighing bottle. The entire tray shall fit inside a desiccator and
butyryl content, dissolve the sample by either of the following
should have a basket-type handle to facilitate the introduction
two methods:
and removal of the tray (convenient but not essential).
22.3.1 Gently rotate the flask by hand to distribute and
20.3 Buret, automatic zero, 35-mL, 25-mL bulb, stem
spread the sample in a thin layer over the bottom of the flask.
graduated from 25 to 35 mL in 0.05-mL increments; or pipet,
Add 70 mL of acetone to the flask and swirl gently until the
automatic zero, 30-mL for NaOH solution (40 g/L).
sample particles are completely wetted and evenly dispersed.
20.4 Buret, automatic zero, 15-mL, 10-mL bulb, stem
Stopper the flask and allow it to stand undisturbed for 10 min.
graduated from 10 to 15 mL in 0.05-mL increments, for 1 N
Carefully add 30 mL of dimethyl sulfoxide from a graduate to
H SO .
2 4
the flask, pouring the solvent down the sides of the flask to
20.5 Buret, 5-mL, in 0.01 or 0.1-mL divisions, for back
wash down any sample particles clinging to the side. Stopper
titration with 0.1 N NaOH solution.
the flask and allow it to stand with occasional swirling until
20.6 Magnetic Stirrer, for single flask.
solution is complete. Magnetic stirring or gentle mechanical
20.7 Magnetic Stirrer, capacity twelve or more flasks.
agitation that will not splash the solution is recommended.
20.8 Stirring Bars, stainless steel Type 416, length 50 mm,
When solution appears to be complete, add 50 mL of acetone
diameter 5 to 6 mm or equivalent, dimensions not critical.
and swirl or stir for 5 min. Proceed in accordance with 22.4.
21. Reagents
22.3.2 Dimethyl sulfoxide is the preferred solvent, but if it
is not available, spread the sample in a thin layer over the
21.1 Acetone—Add one 30-mL portion of 1.0 N NaOH
bottom of the flask, add 15 mL of acetone, swirl to wet the
solution to a mixture of 150 mL acetone and 100 mL hot water,
particles with acetone, stopper the flask, and allow the mixture
allow to stand with frequent swirling for 30 min, and titrate
to stand undisturbed for 20 min. Add 75 mL of pyridine
with 1.0 N H SO . Add another 30-mL portion of 1.0 N NaOH
2 4
without shaking or swirling and allow the mixture to stand for
solution to 100 mL of hot water, allow to stand for 30 min, and
10 min. Heat the solution just to boiling and swirl or stir for 5
titrate as above. The difference between the two titrations shall
min. Again heat to boiling and swirl or stir for 10 min.
not exceed 0.05 mL.
Continue to heat and stir until the mixture is homogeneous and
21.2 Dimethyl Sulfoxide.
all large gel masses are broken down into individual highly
21.3 Pyridine.
swollen particles. When these highly swollen gel particles are
21.4 Sodium Hydroxide Solution (40 g/L)—Dissolve 40 g of
well dispersed and are not fused together in large gel masses,
sodium hydroxide (NaOH) in water and dilute to 1 L.
no further heating is necessary. Cool the flask, add 30 mL of
21.5 Sodium Hydroxide, Standard Solution (0.1 N)—
acetone, and swirl or stir for 5 min.
Prepare and standardize a 0.1 N solution of NaOH.
21.6 Sulfuric Acid Standard (1.0 N)—Prepare and stan- 22.4 Add 30 mL of NaOH solution (40 g/L) with constant
swirling or stirring to the solution of the sample and also to the
dardize a 1.0 N solution of sulfuric acid (H SO ).
2 4
21.7 Phenolphthalein Indicator Solution (1 g/100 mL)— blank. Use of a magnetic stirrer is recommended (Note 2). It is
absolutely necessary that a finely divided precipitate of regen-
Dissolve1gof phenolphthalein in 100 mL of ethyl alcohol
(95 %). erated cellulose, free of lumps, be obtained. Stopper the flask
and let the mixture stand with occasional swirling or stir on the
22. Procedure
magnetic stirring unit. Allow 30 min for saponification of
22.1 Dry the ground well-mixed sample in weighing bottle lower acetyl samples, 2 h for high acetyl samples when
for2hat105 6 3°C and weigh 1.9 6 0.05 g of the dried dimethyl sulfoxide is the solvent, and 3 h when pyridine is the
sample by difference to the nearest 1 mg into a 500-mL solvent. At the end of the saponification period, add 100 mL of
Erlenmeyer flask. Prepare a blank by drying approximately 3.8 hot water, washing down the sides of the flask, and stir for 1 or
g of potassium acid phthalate and weighing it by difference into 2 min. Add 4 or 5 drops of phenolphthalein indicator solution
a flask a
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