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: D817 − 12

Standard Test Methods of Testing

Cellulose Acetate Propionate and Cellulose Acetate
Butyrate1
This standard is issued under the fixed designation D817; 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 D2929 Test Method for Sulfur Content of Cellulosic Mate-

1.1 These test methods cover procedures for the testing of rials by X-Ray Fluorescence
cellulose acetate propionates and acetate butyrates. These D5897 Test Method for Determination of Percent Hydroxyl
esters may vary widely in composition and properties, so on Cellulose Esters by Potentiometric Titration—
certain of the procedures can be used only in the ranges of Alternative Method
composition where they are suitable. 3. Reagents
1.2 The values stated in SI units are to be regarded as the 3.1 Purity of Reagents—Reagent grade chemicals shall be
standard. The values given in parentheses are for information used in all tests. Unless otherwise indicated, it is intended that
only. all reagents shall conform to the specifications of the Commit-
1.3 The test procedures appear in the following sections: tee on Analytical Reagents of the American Chemical Society,
Sections where such specifications are available.3 Other grades may be
Acetyl Propionyl or Butyryl Contents 28 – 37 used, provided it is first ascertained that the reagent is of
Acetyl Content, Apparent 18 – 27
Acidity, Free 12 – 17
sufficiently high purity to permit its use without lessening the
Ash 7 – 10 accuracy of the determination.
Color and Haze 77 – 81
Heat Stability 57 – 65 4. Conditioning
Hydroxyl Content 38 – 44
Hydroxyl Content, Primary 46 – 50 4.1 Conditioning—Condition the test specimens at 23 6
Intrinsic Viscosity 67 – 71
2°C (73.4 6 3.6°F) and 50 6 5 % relative humidity for not less
Moisture Content 5-6
Sulfur or Sulfate Content 51 – 56 than 40 h prior to test in accordance with Procedure A of
Viscosity 74-75 Practice D618, for those tests where conditioning is required.
Limiting Viscosity Number 67 – 71
In cases of disagreement, the tolerances shall be 61°C
1.4 This standard does not purport to address the safety (61.8°F) and 62 % relative humidity.
concerns, if any, associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety and 4.2 Test Conditions—Conduct tests in the Standard Labora-
health practices and determine the applicability of regulatory tory Atmosphere of 23 6 2°C (73.4 6 3.6°F) and 50 6 5 %
limitations prior to use. relative humidity, unless otherwise specified in the test meth-
ods. In cases of disagreements, the tolerances shall be 61°C
2. Referenced Documents (61.8°F) and 62 % relative humidity.
2.1 ASTM Standards:2 MOISTURE CONTENT
D618 Practice for Conditioning Plastics for Testing
D1343 Test Method for Viscosity of Cellulose Derivatives 5. Procedure
by Ball-Drop Method 5.1 Transfer about 5 g of the sample to a tared, low,
wide-form weighing bottle and weigh to the nearest 0.001 g.
1
Dry in an oven for 2 h at 105 6 3°C. Remove the bottle from
These test methods are under the jurisdiction of ASTM Committee D01 on
Paint and Related Coatings, Materials, and Applications and are the direct the oven, cover, cool in a desiccator, and weigh.
responsibility of Subcommittee D01.36 on Cellulose and Cellulose Derivatives.
Current edition approved Nov. 1, 2012. Published January 2013. Originally
3
approved in 1944. Last previous edition approved in 2010 as D817 – 96 (2010). Reagent Chemicals, American Chemical Society Specifications, American
DOI: 10.1520/D0817-12. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or listed by the American Chemical Society, see Analar Standards for Laboratory
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
Standards volume information, refer to the standard’s Document Summary page on and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
the ASTM website. MD.

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 D817 − 12
6. Calculation 12.3 Phenolphthalein Indicator Solution (1 g/100 mL)—
6.1 Calculate the percentage of moisture as follows: Dissolve 1 g phenolphthalein in 100 mL of ethyl alco-
hol (95 %).
Moisture, % 5 ~ A/B ! 3 100 (1)
12.4 Sodium Hydroxide, Standard Solution (0.01 N)—
where: Prepare and standardize a 0.01 N solution of sodium hydroxide
A = weight loss on heating, g, and (NaOH).
B = sample used, g.
Test Method A—For Samples Containing Not More than
ASH About 30 % Propionyl or Butyryl
7. Significance and Use 13. Procedure
7.1 Ash content gives an estimate of the inorganic content 13.1 Shake 5 g of the sample, corrected for moisture content
of cellulose ester samples. The presence of high levels of if necessary, in a 250-mL Erlenmeyer flask with 150 mL of
inorganic content (ash) can be detrimental to the melt stability freshly boiled, cold water. Stopper the flask and allow it to
and optical clarity of a cellulose ester in melt processing or act stand for 3 h. Filter off the cellulose ester and wash it with
as a potential source of insolubles when the ester is used in water. Titrate the combined filtrate and washings with 0.01 N
solution. NaOH solution, using phenolphthalein indicator solution.
8. Procedure 13.2 Run a blank determination on the water, using the same
volume as was used in extracting the sample.
8.1 Dry the sample for 2 h at 105 6 3°C and weigh 10 to 50
g, to the nearest 0.01 to 0.1 g, depending on its ash content and 14. Calculation
the accuracy desired. Burn directly over a flame in a 100-mL
tared platinum crucible that has been heated to constant weight 14.1 Calculate the percentage of acidity as free acetic acid
and weighed to the nearest 0.1 mg. Add the sample in portions as follows:
if more than 10 g is taken. The sample should burn gently and Free acetic acid, % 5 $ @ ~ A 2 B ! C 3 0.06# /W % 3 100 (3)
the portions should be added as the flame subsides. Continue
where:
heating with a burner only as long as the residue burns with a
flame. Transfer the crucible to a muffle furnace and heat at 550 A = NaOH solution used to titrate the sample, mL,
to 600°C for 3 h, or longer if required, to burn all the carbon. B = NaOH solution used to titrate the blank, mL,
Allow the crucible to cool and then transfer it, while still warm, C = normality of the NaOH solution, and
W = sample used, g.
to a desiccator. When the crucible has cooled to room
temperature, weigh accurately to the nearest 0.1 mg. Test Method B—For Samples Containing More than About
7 %Propionyl or Butyryl and Particularly Suitable for
9. Calculation
Samples Containing More than 30 % Propionyl or Butyryl
9.1 Calculate the percentage of ash as follows:
Ash, % 5 ~ A/B ! 3 100 (2) 15. Procedure

where: 15.1 Dissolve 10.0 g of the sample, corrected for moisture

content if necessary, in 200 mL of neutral acetone plus 20 mL
A = ash, g, and of water. When completely dissolved, add 50 mL of water and
B = sample used, g.
shake well to precipitate the ester in a finely divided form. Add
10. Precision and Bias 3 drops of methyl red indicator solution and titrate to a
lemon-yellow end point and 0.01 N NaOH solution.
10.1 No statement on bias can be made as no reference
material is available as a standard. 15.2 Make a blank determination on the reagents.

FREE ACIDITY 16. Calculation

16.1 Calculate the free acid content as acetic acid as
11. Significance and Use
directed in Section 14.
11.1 Free acidity is a measure of unesterified organic acid in
the ester. The presence of high levels of free acid is potentially 17. Precision and Bias
detrimental to melt processing of the ester and can impact the
17.1 No statement on bias can be made as no reference
odor of the ester.
material is available as a standard.
12. Reagents APPARENT ACETYL CONTENT
12.1 Acetone, neutral.
12.2 Methyl Red Indicator Solution (0.4 g/L)—Dissolve 0.1 18. Scope
g of methyl red in 3.72 mL of 0.1000 N NaOH solution and 18.1 The test methods described in the following Sections
dilute to 250 mL with water. Filter if necessary. 20 to 26 cover the determination of the saponification value of

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 D817 − 12
the sample calculated as percentage of apparent acetyl, equiva- 21.6 Sulfuric Acid Standard (1.0 N)—Prepare and standard-
lent weight 43. This value is required in the calculation of ize a 1.0 N solution of sulfuric acid (H2SO4).
acetyl and propionyl or butyryl contents in 36.1.
21.7 Phenolphthalein Indicator Solution (1 g/100 mL)—
18.2 The test method used should be specified or agreed Dissolve 1 g of phenolphthalein in 100 mL of ethyl alcohol
upon. The choice depends on the propionyl or butyryl content (95 %).
and the physical condition of the sample. Ordinarily, Test
Method A is recommended for samples having less than about 22. Procedure
35 % propionyl or butyryl and Test Method B for samples
having more than that amount. 22.1 Dry the ground well-mixed sample in weighing bottle
for 2 h at 105 6 3°C and weigh 1.9 6 0.05 g of the dried
19. Significance and Use sample by difference to the nearest 1 mg into a 500-mL
19.1 Apparent acetyl content is a measure of the saponifi- Erlenmeyer flask. Prepare a blank by drying approximately 3.8
cation value of the ester. Apparent acetyl value is required in g of potassium acid phthalate and weighing it by difference into
the calculation of acetyl, propionyl, and butyryl content in a flask as described above. Carry the blank through the entire
36.1. procedure.
NOTE 1—Potassium acid phthalate is used so that the concentration of
Test Method A—For Samples Containing Less than About the NaOH in contact with the solvent in the blank will be approximately
35 % Propionyl or Butyryl the same as that in contact with the sample and so that the titration of the
blank will be approximately the same as the titration of the sample, thus
20. Apparatus avoiding errors caused by using a different buret for the titration of the
20.1 Weighing Bottle, glass-stoppered, 15-mL capacity, blank and the sample or by refilling the 15-mL buret. If desired, however,
the potassium acid phthalate may be omitted.
25-mm diameter by 50 mm high.
20.2 Tray, copper or aluminum, approximately 137 mm 22.2 For acetone-soluble sample, put the sample into solu-
square, containing 25 compartments 25 mm square. Each tion as follows: Add 150 mL of acetone and 5 to 10 mL of
compartment shall have the correct dimensions to contain one water and swirl to mix. Stopper the flask and allow it to stand
weighing bottle. The entire tray shall fit inside a desiccator and with occasional swirling until solution is complete. Solution
should have a basket-type handle to facilitate the introduction may be hastened by magnetic stirring or by any suitable
and removal of the tray (convenient but not essential). mechanical shaking that will provide a gentle rocking type of
agitation to avoid splashing the solution on the stopper. It is
20.3 Buret, automatic zero, 35-mL, 25-mL bulb, stem essential that complete solution be effected.
graduated from 25 to 35 mL in 0.05-mL increments; or pipet,
automatic zero, 30-mL for NaOH solution (40 g/L). 22.3 For acetone-insoluble samples of low propionyl or
butyryl content, dissolve the sample by either of the following
20.4 Buret, automatic zero, 15-mL, 10-mL bulb, stem
two methods:
graduated from 10 to 15 mL in 0.05-mL increments, for 1 N
H2SO4. 22.3.1 Gently rotate the flask by hand to distribute and
spread the sample in a thin layer over the bottom of the flask.
20.5 Buret, 5-mL, in 0.01 or 0.1-mL divisions, for back Add 70 mL of acetone to the flask and swirl gently until the
titration with 0.1 N NaOH solution. sample particles are completely wetted and evenly dispersed.
20.6 Magnetic Stirrer, for single flask. Stopper the flask and allow it to stand undisturbed for 10 min.
Carefully add 30 mL of dimethyl sulfoxide from a graduate to
20.7 Magnetic Stirrer, capacity twelve or more flasks.
the flask, pouring the solvent down the sides of the flask to
20.8 Stirring Bars, stainless steel Type 416, length 50 mm, wash down any sample particles clinging to the side. Stopper
diameter 5 to 6 mm or equivalent, dimensions not critical. the flask and allow it to stand with occasional swirling until
21. Reagents solution is complete. Magnetic stirring or gentle mechanical
agitation that will not splash the solution is recommended.
21.1 Acetone—Add one 30-mL portion of 1.0 N NaOH When solution appears to be complete, add 50 mL of acetone
solution to a mixture of 150 mL acetone and 100 mL hot water, and swirl or stir for 5 min. Proceed in accordance with 22.4.
allow to stand with frequent swirling for 30 min, and titrate 22.3.2 Dimethyl sulfoxide is the preferred solvent, but if it
with 1.0 N H2SO4. Add another 30-mL portion of 1.0 N NaOH is not available, spread the sample in a thin layer over the
solution to 100 mL of hot water, allow to stand for 30 min, and bottom of the flask, add 15 mL of acetone, swirl to wet the
titrate as above. The difference between the two titrations shall particles with acetone, stopper the flask, and allow the mixture
not exceed 0.05 mL. to stand undisturbed for 20 min. Add 75 mL of pyridine
21.2 Dimethyl Sulfoxide. without shaking or swirling and allow the mixture to stand for
21.3 Pyridine. 10 min. Heat the solution just to boiling and swirl or stir for 5
min. Again heat to boiling and swirl or stir for 10 min.
21.4 Sodium Hydroxide Solution (40 g/L)—Dissolve 40 g of Continue to heat and stir until the mixture is homogeneous and
sodium hydroxide (NaOH) in water and dilute to 1 L. all large gel masses are broken down into individual highly
21.5 Sodium Hydroxide, Standard Solution (0.1 N)— swollen particles. When these highly swollen gel particles are
Prepare and standardize a 0.1 N solution of NaOH. well dispersed and are not fused together in large gel masses,

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 D817 − 12
no further heating is necessary. Cool the flask, add 30 mL of Test Method B—For Cellulose Esters Containing More than
acetone, and swirl or stir for 5 min. 30 % Propionyl or Butyryl, by Varying the Reagents4
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 24. Reagents
blank. Use of a magnetic stirrer is recommended (Note 2). It is 24.1 Acetone–Alcohol Mixture—Mix equal volumes of ac-
absolutely necessary that a finely divided precipitate of regen- etone and methyl alcohol.
erated cellulose, free of lumps, be obtained. Stopper the flask 24.2 Hydrochloric Acid, Standard (0.5 N)—Prepare and
and let the mixture stand with occasional swirling or stir on the standardize a 0.5 N solution of hydrochloric acid (HCl).
magnetic stirring unit. Allow 30 min for saponification of
lower acetyl samples, 2 h for high acetyl samples when 24.3 Phenolphthalein Indicator Solution (1 g/100 mL)—
dimethyl sulfoxide is the solvent, and 3 h when pyridine is the Dissolve 1 g of phenolphthalein in 100 mL of ethyl alcohol
solvent. At the end of the saponification period, add 100 mL of (95 %).
hot water, washing down the sides of the flask, and stir for 1 or 24.4 Pyridine – Alcohol Mixture—Mix equal volumes of
2 min. Add 4 or 5 drops of phenolphthalein indicator solution pyridine and methyl alcohol.
and titrate the excess NaOH solution with 1.0 N H2SO4 (Note 24.5 Sodium Hydroxide, Aqueous Solution (20 g/L)—
3). Titrate rapidly with constant swirling or stirring until the Dissolve 20 g of sodium hydroxide (NaOH) in water and dilute
end point is reached; then add an excess of 0.2 or 0.3 mL of to 1 L with water.
H2SO4. Allow the mixture to stand with occasional stirring or
preferably stir on the magnetic stirrer for at least 10 min. Then 24.6 Sodium Hydroxide, Methanol Solution (20 g/L)—
add 3 drops of phenolphthalein indicator solution to each flask Dissolve 20 g of NaOH in 20 mL of water and dilute to 1 L
and titrate the same excess of acid with 0.1 N NaOH solution with methyl alcohol.
to a persistent phenolphthalein end point. Take extreme care to
locate this end point; after the sample is titrated to a faint pink 25. Procedure
end point, swirl the mixture vigorously or place it for a moment 25.1 Dry the sample for 2 h at 105 6 3°C and cool in a
on the magnetic stirrer. If the end point fades because of acid desiccator. Weigh 0.5-g portions of the sample to the nearest
soaking from the cellulose, continue the addition of 0.1 N 0.005 g and transfer to 250-mL glass-stoppered Erlenmeyer
NaOH solution until a faint persistent end point remains after flasks. Dissolve each sample in 100 mL of appropriate solvent
vigorous swirling or stirring. Titrate the blank in the same (see 25.2 and 25.3) and prepare at least two blanks, which shall
manner as the sample. be carried through all steps of the procedure.
NOTE 2—While the amount of magnetic stirring is somewhat optional, 25.2 Samples Containing 30 to 45 % Propionyl or Butyryl—
such stirring during the entire period of the determination is strongly Dissolve in 100 mL of the acetone–alcohol mixture. Add water
recommended. Solution is more rapid, titrations are more rapid, and the and aqueous NaOH solution from a buret or pipet in the
end point can be approached directly and without a back titration.
NOTE 3—It is important to correct all 1.0 N H2SO4 buret readings for following order and swirl the contents of the flask vigorously
temperature and buret corrections. during all additions: 10 mL of NaOH solution, 10 mL of water,
10 mL of NaOH solution, 5 mL of water, 20 mL of NaOH
23. Calculation solution, and 5 mL of water. Stopper and allow to stand at room
temperature for 16 to 24 h.
23.1 Calculate the percentage by weight of acetyl as follows
(see Note 4): 25.3 Samples Containing More than 45 % Propionyl or
Butyryl—Dissolve in 100 mL of the pyridine–alcohol mixture.
Acetyl, % 5 $ @ ~ D 2 C ! N a 2 ~ B 2 A ! N b 1P # 3 0.04305% /W 3 100
Add 30 mL of the methanol solution of NaOH from a pipet or
(4)
buret slowly, with swirling. Add 20 mL of water slowly in
P 5 ~ GH 3 1000! /204.2 about 2-mL portions, with swirling, and swirl the flask until the
solution becomes turbid. Stopper and allow to stand overnight
where: at room temperature.
A = NaOH solution required for titration of the sample, mL, 25.4 Back-titrate the excess NaOH with 0.5 N HCl just to
B = NaOH solution required for titration of the blank, mL, the disappearance of color, using phenolphthalein indicator
Nb = normality of the NaOH solution,
solution.
C = H2SO4 required for titration of the sample, mL
D = H2SO4 required for titration of the blank, mL,
Na = normality of the H2SO4, 26. Calculation
P = milliequivalents of potassium acid phthalate, 26.1 Calculate the apparent acetyl content as follows:
G = potassium acid phthalate used, g,
Apparent acetyl, % 5 $ @ ~ A 2 B ! N a 3 0.04305# /W % 3 100 (5)
H = purity factor for potassium acid phthalate, and
W = sample used, g.
NOTE 4—When equal volumes of alkali or acid are added to samples
and blank, these amounts cancel out. Thus only the amounts of each added 4
Malm, C. J., Genung, L. B., Williams, R. F., Jr., and Pile, M. A., “Analysis of
in the titration enter into the calculations. Use of potassium acid phthalate Cellulose Derivatives: Total Acyl in Cellulose Organic Esters by Saponification in
in the blank is recommended. When it is not used, the term P drops out of Solution,” Industrial and Engineering Chemistry, Analytical Edition, IENAA, Vol
the equation. 16, 1944, pp. 501–504.

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 D817 − 12
where:
A = HCl required for titration of the blank, mL,
B = HCl required for titration of the sample, mL,
Na = normality of the HCl, and
W = sample used, g.

27. Precision and Bias

27.1 No statement on bias can be made as no reference
material is available as a standard.
ACETYL AND PROPIONYL OR BUTYRYL
CONTENTS

28. Scope
28.1 The test methods described in the following Sections
30 to 36 cover the determination of acetyl and propionyl or
butyryl contents of cellulose mixed esters by calculation from
the apparent acetyl content, determined in accordance with
Sections 18 to 26, and the molar ratio of acetyl and propionyl
or butyryl, determined in accordance with Sections 30 to 35.
The molar ratio of acetyl and propionyl or butyryl is deter-
mined by saponifying, acidifying, vacuum distilling off the
mixture of acids, and determining the distribution ratio of the
acids between n-butyl acetate and water. The distribution ratios
are also determined for acetic, propionic, and butyric acids,
using samples of known high purity, and the molar ratio of the
acids in the sample is calculated from these values.5 A—Flask containing sample (500-mL, round-bottom).
B—Capillary inlet tube.
28.2 The saponification conditions are varied depending on C—Kjeldahl distilling head.
D—Condenser.
the propionyl or butyryl content of the sample. Use Procedure E—Receiver (500-mL distilling flask).
A (Section 32) for samples containing less than about 35 % F—Opening for adding water.
propionyl or butyryl, and use Procedure B (Section 33) for G—Water bath for heating sample.
H—Cooling bath for receiver.
samples containing more than that amount. I—Side arm, connected to vacuum line.
28.3 Analyses for combined acetic, propionic, and butyric FIG. 1 Vacuum Distillation Apparatus for Mixed-Ester Analysis
acids may be done by gas chromatographic methods. Difficul-
ties encountered include ghosting in the columns, variation of very small capillary inlet tube, B, and a Kjeldahl distilling
factors with composition, and inconsistencies in the use of pure head, C. The Kjeldahl distilling head shall be connected to a
acids as standards. When such methods are used for this vertical condenser, D, having an outlet tube long enough to
purpose, they shall be cross checked with the following reach within 76.2 mm of the bottom of the 500-mL distilling
partition method using suitable check batches to establish flask, E, used as a receiver. The Kjeldahl distilling head shall be
accuracy. equipped with a funnel or stoppered opening, F, for adding
extra water during the distillation. A water bath, G, for heating
29. Significance and Use
the sample and a cooling bath, H, for cooling the receiver shall
29.1 Acetyl and propionyl or butyryl content is a measure of be provided.
the amount of each of these acids esterified onto the cellulose
backbone of the polymer. The amount of substitution of these 31. Reagents
esters has a very strong effect on the polymer’s solubility and 31.1 Acetic, Propionic, and Butyric Acids—Acetic,
physical properties. propionic, and butyric acids of tested purity.
30. Apparatus 31.2 Bromcresol Green Indicator Solution (0.4 g/L)—Grind
0.1 g of tetrabromo-m-cresolsulfonphthalein in a mortar with
30.1 Vacuum Distillation Apparatus—The vacuum distilla-
14.3 mL of 0.01 N NaOH solution and dilute to 250 mL.
tion apparatus shown in Fig. 1 will be required. The 500-mL
round-bottom flask, A, shall be fitted with a stopper carrying a 31.3 n-Butyl Acetate—Prepare n-butyl acetate for use as an
extraction solvent, free of acidity and water and containing not
more than 2 % butyl alcohol. Check for acidity by shaking 60
5
Malm, C. J., Nadeau, G. F., and Genung, L. B., “Analysis of Cellulose mL of the n-butyl acetate with 30 mL of water in a 125-mL
Derivatives: Analysis of Cellulose Mixed Esters by the Partition Method,” Indus-
separatory funnel for about 1 min. Allow to settle, draw off the
trial and Engineering Chemistry, Analytical Edition, IENAA, Vol. 14, 1942, pp.
292–297. This reference may be consulted for application to other mixed esters and water layer, and titrate with 0.1 N NaOH solution, using
to three-component mixtures. phenolphthalein as the indicator. If this requires more than 0.02

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 D817 − 12
mL of 0.1 N NaOH solution, the butyl acetate should be 33.3 Add the required amount, about 50 mL, of H3PO4
purified or a correction for acidity applied to each titration. (1 + 14) to form monosodium phosphate, which liberates the
31.4 Ethyl Alcohol, Formula 2B, 3A, or 30 (denatured). organic acids from their sodium salts. Also add 100 mL of
water to each flask and reassemble the distillation apparatus.
31.5 Phosphoric Acid (1 + 14)—Dilute 68 mL of phos- Vacuum-distill the volatile acids as described in 32.2.
phoric acid (H3PO4, 85 %) to 1 L with water. Titrate the NaOH
solution (20 g/L) with this acid to a yellow end point, using 33.4 Continue as directed in Section 34.
bromcresol green indicator solution, and calculate the volume
Determination of the Molar Ratios of the Acids
of the acid (approximately 50 mL) required for 100 mL of the
NaOH solution.
34. Procedure
31.6 Sodium Hydroxide Solution (20 g/L)—Dissolve 20 g of
sodium hydroxide (NaOH) in water and dilute to 1 L. 34.1 Titrate a 25-mL portion of the distillate (32.2) with 0.1
N NaOH solution, using phenolphthalein as the indicator.
31.7 Sodium Hydroxide, Standard Solution (0.1 N)— Designate the volume of NaOH solution required as M. Shake
Prepare and standardize a 0.1 N solution of NaOH. 30 mL of the distillate in a small separatory funnel with 15 mL
Isolation of the Mixed Acids of n-butyl acetate. Measure these volumes accurately using
pipets and burets. Shake the mixture thoroughly for 1 min,
32. Procedure A—For Samples Containing Less than allow the layers to separate for 2 min, and draw off the aqueous
About 35 % Propionyl or Butyryl (lower) layer. Pipet out 25 mL of the solution and titrate with
0.1 N NaOH solution (Note 6). Designate the volume of NaOH
32.1 Heat duplicate 3-g portions of the sample, not espe- solution required as M1. Calculate K, the percentage partition
cially dried nor accurately weighed, with 100 mL of NaOH ratio of the acids in the distillate, as follows:
solution (20 g/L) in 500-mL, round-bottom, chemically resis-
K 5 ~ M 1 /M ! 3 100 (6)
tant glass flasks in a water bath at 40°C for 48 to 72 h. At the
NOTE 6—It should be kept in mind that all these determination are ratios
end of this time add the required amount (approximately 50
and not quantitative; however, accuracy of duplication is very important.
mL) of H3PO4 (1 + 14) to each flask to form monosodium All measurements must be made as exactly as those made by standard-
phosphate, which liberates the organic acids from their sodium izations of the solutions and equipment.
salts.
34.2 In the same manner determine the distribution ratios
32.2 Assemble the vacuum distillation apparatus as illus- for acetic, propionic, and butyric acids. Dilute a sample of each
trated in Fig. 1. Heat the 500-mL round-bottom flask contain- acid of tested purity with water to give an approximately 0.1 N
ing the sample in a water bath, and vacuum-distill the acid solution. Titrate 25-mL portions and extract 30-mL portions,
solutions to dryness, allowing a small stream of air bubbles to following exactly the same procedure as used for the mixtures
enter to avoid bumping. Keep the receiver cooled to 0°C. Add (34.1). Calculate the partition ratios for the pure acids, as
25 mL of water to the residue in each flask and again distill to decimal fractions, as follows (Note 7):
dryness. Repeat the distillation to dryness with a second 25-mL
k 5 M 1 /M (7)
portion of water.
where:
NOTE 5—In this operation it is not necessary to work with quantitative
accuracy at all stages, but it is necessary to obtain water solutions of the ka = distribution ratio for acetic acid under the conditions
acids in the same ratios as they occur in the esters. The volume of the described,
distillate and rinsings is usually 200 to 250 mL, which in the majority of kp = distribution ratio for propionic acid under the condi-
cases automatically adjusts the acidity of the distillate to 0.06 to 0.12 N, tions described, and
the range desired for subsequent extractions.
kb = distribution ratio for butyric acid under the conditions
32.3 Continue as directed in Section 34. described.
NOTE 7—The constants must be checked occasionally and must be
33. Procedure B—For Samples Containing More than determined by each operator for each supply of butyl acetate. Blanks
About 35 % Propionyl or Butyryl should be run on the butyl acetate, since it may develop acidity on
standing, particularly if it contains a little water. All measurements should
33.1 Weigh duplicate 3-g samples, not especially dried nor be made with good pipets or burets and extreme care and cleanliness
accurately weighed, into 500-mL round-bottom flasks and add observed during the whole operation. The accuracy of the procedure can
100 mL of Formula 2B, 3A, or 30 denatured ethyl alcohol and be checked by testing an acid mixture of known composition.
100 mL of NaOH solution (20 g/L) to each flask. Allow the
samples to stand stoppered at room temperature for 48 to 72 h. 35. Calculation
At the end of this period, filter off the regenerated cellulose, 35.1 Calculate the molar ratios of acetic and propionic or
collecting the filtrates in 500-mL round-bottom flasks. butyric acids in the mixed acids as follows (Note 8):
33.2 Assemble the vacuum-distillation apparatus as illus- P 5 ~ 100k a 2 K ! / ~ k a 2 k p ! (8)
trated in Fig. 1. Heat the flasks in the water bath and A 5 100 2 P (9)
vacuum-distill off all the alcohol. After distilling to dryness,
release the vacuum, rinse out the distillation heads, condensers, B 5 ~ 100k a 2 K ! / ~ k a 2 k b ! (10)
and receivers, and discard the distillates and rinsings. A 5 100 2 B (11)

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 D817 − 12
where: HYDROXYL CONTENT
P = percentage of propionic acid, mol,
B = percentage of butyric acid, mol, 38. Scope
A = percentage of acetic acid, mol, 38.1 This test method is applicable to pyridine-soluble
K = percentage distribution ratio of the acids in the distillate cellulose esters and is especially useful when the hydroxyl
(34.1), content is low. (Samples containing plasticizer may be ana-
ka = distribution ratio of acetic acid (34.2), lyzed directly by this test method because the plasticizer is
kp = distribution ratio of propionic acid (34.2), and removed during washing of the carbanilate).
kb = distribution ratio of butyric acid (34.2).
NOTE 8—In order to evaluate two unknowns, two simultaneous 38.2 A preferred method is available in Test Method D5897.
algebraic equations involving the two unknown quantities are necessary.
In the case of a binary acid mixture, the sum of the mol percentages of the 39. Summary of Test Method
acids present represents the total acidity, or 100 %. If A and B represent the
mole percentages of acetic and butyric acids, respectively: 39.1 Hydroxyl in cellulose esters is determined by reaction
with phenyl isocyanate in pyridine solution under anhydrous
A1B 5 100 (12) conditions to form the carbanilate derivative. The derivative is
Aka 1Bkb 5 K (13) then analyzed for its carbanilate content by ultraviolet absorp-
The distribution ratios ka and kb are known and refer to the tion.
pure individual acids, whereas the distribution ratio K refers to
40. Significance and Use
the binary mixture. By solving these equations for B, the
equations given in this section may be derived. 40.1 Hydroxyl content is a measure of the free hydroxyl on
the cellulose backbone of the polymer. Hydroxyl content has a
Calculation of Acetyl, Propionyl, and Butyryl Contents strong effect on the polymer’s solubility and physical proper-
36. Calculation ties. Hydroxyl content also impacts the propensity for this
polymer to crosslink with various crosslinking agents.
36.1 Calculate the percentages by weight of acetyl,
propionyl, and butyryl as follows: 41. Apparatus
Acetyl, % 5 AC/100 (14) 41.1 Spectrophotometer, complete with hydrogen light
Propionyl, % 5 ~ PC/100! 3 ~ 57/43! (15) source and a set of four 1.00-cm quartz cells or an equally
Butyryl, % 5 ~ BC/100! 3 ~ 71/43! (16)
suitable apparatus. The wavelength calibration, as checked
against a mercury lamp, shall be within the manufacturer’s
where: tolerances. As a further check, measure the density of a
A = percentage of acetic acid (Section 35), mol, potassium chromate (K2CrO4) solution prepared as follows:
P = percentage of propionic acid (Section 35), mol, Dissolve 0.0400 g of K2CrO4 or 0.0303 g of potassium
B = percentage of butyric acid (Section 35), mol, and dichromate (K2Cr2O7) in 0.05 N potassium hydroxide (KOH)
C = percentages by weight of apparent acetyl (Sections 23 solution and dilute to 1 L in a volumetric flask with 0.05 N
and 26). KOH solution. Using the hydrogen lamp measure the absor-
36.2 Hydroxyl can be measured precisely, particularly at bance at 280 nm of a silica cell filled with the K2CrO4 solution
high degrees of esterification (Sections 38 to 44). It is therefore and also of the same cell filled with water. The absorbance of
sometimes advantageous to base the calculation of weight the solution minus that of the blank shall be 0.723 6 0.023.
percentages of acetyl, propionyl, and butyryl on hydroxyl 41.2 Bottles, 112-g (4-oz), with screw caps, for washing the
content rather than on apparent acetyl as in 36.1. The equations samples.
for this calculation are as follows:
For cellulose acetate propionates: 41.3 Special Reflux Tubes for the carbanilation, constructed
as follows (see Fig. 2): Make a test tube approximately 20 by
Acetyl, % 5 9.15A ~ 31.5 2 h ! / ~ 786 2 A ! (17) 150 mm from the outer part of a standard-taper 24/40 ground-
Propionyl, % 5 2.93P ~ 31.5 2 h ! / ~ 786 2 A ! (18) glass joint by closing the open end in a blast lamp. Draw the
For cellulose acetate butyrates: tubing on the inner joint to a constriction just above the joint.
Cut the glass at the point and seal on a short length of 8-mm
Acetyl, % 5 4.88A ~ 31.5 2 h ! / ~ 443 2 A ! (19) tubing to provide a bearing for a glass stirrer. Make a stirrer of
Butyryl, % 5 8.05B ~ 31.5 2 h ! / ~ 443 2 A ! (20) 4-mm glass rod with a semicircle at right angles to the shaft at
where, in addition to the definitions of terms in 36.1: the bottom and small enough to fit into the test tube. When
h = weight percentage of hydroxyl (Section 44). properly constructed this unit acts as an air condenser, thus
preventing the loss of solvent by evaporation.
NOTE 9—This calculation involves the assumption that there are exactly
three hydroxyls, free plus esterified, for each anhydroglucose unit of 41.4 Pipet, serological type, 5-mL capacity, graduated in
cellulose. 0.1-mL divisions.
37. Precision and Bias 41.5 Büchner Funnel, of a size accommodating 90-mm
37.1 No statement on bias can be made as no reference filter paper.
material is available as a standard. 41.6 Automatic Shaker, with speed regulator mechanism.

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 D817 − 12
43. Procedure
43.1 In the following procedure the phenyl isocyanate
reagent shall be used under anhydrous conditions. Therefore,
the sample, containers, pipet, and all other equipment shall be
thoroughly dried.
43.2 Place a 0.5-g sample in a special reflux tube and dry in
an electric oven at 105 6 3°C for 2 h. Remove the tube from
the oven, add 5 mL of pyridine, assemble the reflux apparatus
complete with glass stirring rod, and place in the 115 to 120°C
oil bath. Stir occasionally until the sample is completely
dissolved. Add 0.5 mL of phenyl isocyanate, stir thoroughly,
and reflux in the oil bath for 1⁄2 h to complete the reaction. Use
0.1 mL of phenyl isocyanate for each 1 % of estimated
hydroxyl content, but never less than 0.5 mL.
43.3 At the end of the reaction time, remove the sample and
dilute it with acetone to the proper viscosity for precipitation.
The amount of acetone used to thin the solution is a critical
factor in acquiring a good precipitate. Samples having low
viscosity require little, if any, dilution. The average sample
requires the addition of about an equal volume of acetone.
Precipitate the carbanilate by pouring the solution into about
200 mL of ethyl alcohol, or if the ester contains more than
20 % propionyl or butyryl, into the same volume of cold 80 %
alcohol. Stir the alcohol vigorously during the precipitation.
The precipitate should be fluffy and white. Sticky precipitates
indicate too little dilution. Filter off the precipitate using paper
on a Büchner funnel, with suction applied only as long as is
FIG. 2 Special Reflux Tube for Carbanilation necessary to remove the bulk of the solvent; prolonged suction
may cause undesirable clumping together of the precipitate.
43.4 Wash the precipitate with alcohol, unless the sample
41.7 Electric Oven, maintained at 105 6 3°C.
was precipitated in cold 80 % alcohol. In this case, wash the
41.8 Oil Bath, equipped with a rack to hold several of the precipitate in cold 90 % alcohol. Washing is best accomplished
special reflux tubes. This bath shall be kept between 115 and by transferring the precipitate to a 4-oz screw cap bottle
120°C. containing about 75 mL of alcohol and shaking for 1⁄2 h on an
automatic shaker. Filter, pressing out as much liquid as
42. Reagents possible with a glass stopper. Repeat the washing and filtering
42.1 Acetone. operations twice more.
42.2 Ethyl Alcohol, Formula 2B, 3A, or 30 (denatured). NOTE 10—Samples of high hydroxyl content and large amounts of
propionyl or butyryl may give gummy precipitates when poured into cold
42.3 Methylene Chloride–Methyl Alcohol Mixture—Mix 9 80 % alcohol. Samples of this type give improved precipitates when
parts by weight of methylene chloride with 1 part of methyl precipitated in the reverse manner. Pour the diluted reaction solution into
alcohol. This mixture should have an absorbance of less than a 600-mL beaker, taking care to distribute the solution evenly on the
0.2 at 280 nm in a 1.00-cm silica cell measured against air. bottom. Chill the beaker in a brine bath for 30 to 60 s. Pour about 200 mL
of cold 80 % alcohol onto the chilled liquid. Wash the resulting precipitate
Pure methylene chloride has an absorbance of about 0.05, but
and filter in the usual manner using cold 90 % alcohol.
the commercial product may have an absorbance as high as
1.00. The methylene chloride and methyl alcohol should be 43.5 Allow the precipitate to air-dry 1 to 2 h at room
selected to have low absorbance; otherwise, they should be temperature with good ventilation or preferably overnight to
redistilled. ensure complete removal of the alcohol. (Samples wet with
alcohol may sinter and stick to paper or glass when dried at
42.4 Phenyl Isocyanate. 105°C.) Dry the sample at 105°C in the oven for 1 h and cool
42.5 Pyridine, redistilled, of low water content, preferably in a desiccator. Small manila envelopes are convenient for
less than 0.05 %. drying and cooling the samples.

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 D817 − 12
43.6 Weigh 0.1231 g of the dry precipitate into a 100-mL 49. Procedure
volumetric flask fitted with a ground-glass stopper. Add 60 to 49.1 The reagents must be used under anhydrous condi-
80 mL of methylene chloride-methyl alcohol mixture, and tions. It is imperative that the sample and all equipment be
shake occasionally until complete solution occurs. Dilute to thoroughly dry.
100 mL and mix thoroughly. Using the spectrophotometer with
a 1-cm silica cell, measure the absorbance of the solution at 49.2 Place a 0.5-g sample in the test tube of the special
280 nm against the solvent mixture as a reference. reflux apparatus and dry for 2 h at 105 6 3°C. Add 5 mL of
pyridine, insert the top of the reflux apparatus and the stirring,
44. Calculations and heat with stirring in a 115 to 120°C oil bath. After the
sample has dissolved, add 0.5 g of trityl chloride. If the total
44.1 Calculate the percentage of carbanilate, c, for a sample
hydroxyl content exceeds 3 %, use an additional 0.075 g of
weight of 0.1231 g as follows:6
trityl chloride for each additional 1 % hydroxyl. Stir the
Carbanilate, % 5 A 3 17.1 (21) mixture thoroughly and reflux in the oil bath for exactly 2 h at
where: 115 to 120°C. Remove the tube and cool.
A = absorbance. 49.3 Dilute the sample with acetone to the proper viscosity
44.2 Calculate the percentage of hydroxyl as follows: for precipitation. The amount of acetone used to thin the
solution is a critical factor in obtaining a good precipitate.
Hydroxyl, % 5 14.3c/ ~ 100 2 c ! (22) Samples having low viscosity require little, if any, dilution. The
average sample requires the addition of about an equal volume
45. Precision and Bias of acetone. Precipitate the trityl derivative by pouring the
45.1 No statement on bias can be made as no reference solution into about 200 mL of ethyl alcohol with vigorous
material is available as a standard. stirring. The precipitate should be fluffy and white. Sticky
precipitates indicate too little dilution. Separate the precipitate
PRIMARY HYDROXYL CONTENT by filtering through paper on a Büchner funnel, with suction
applied only as long as necessary to remove the bulk of the
46. Summary of Test Method
solvent; prolonged suction may evaporate the alcohol and
46.1 The primary hydroxyl content of cellulose ester is cause the precipitate to partially redissolve in the remaining
determined by formation of the triphenylmethyl (trityl) ether pyridine.
and measurement of the trityl group by ultraviolet absorbance.6
49.4 Wash the precipitate by transferring it to a 4-oz screw
Trityl chloride reacts preferentially with primary hydroxyls.
cap bottle containing 75 mL of ethyl alcohol, capping securely,
Since there is also a slight reaction with secondary hydroxyls,
and shaking for 1⁄2 h on a shaker at medium speed. Again
standardized reaction conditions are important.7
collect the precipitate on a Büchner funnel, pressing out as
47. Apparatus much liquid as possible with a glass stopper. Repeat this
washing and filtering operation twice more, or until the
47.1 See Section 41. absorbance of the filtrate at 259 nm is about the same as that of
an alcohol blank. Allow the precipitate to air-dry on the filter
48. Reagents paper for 1⁄2 h at room temperature with good ventilation, or
48.1 Acetone. preferably overnight, to remove most of the alcohol. (Samples
48.2 Ethyl Alcohol, Formula 2B, 3A, or 30 (denatured). wet with alcohol may sinter or stick to paper or glass when
dried at 105°C). Transfer the sample to a manila envelope, dry
48.3 Methylene Chloride-Methyl Alcohol Mixture—Mix 9 it for 1 h at 105°C, and cool in a desiccator.
parts by weight of methylene chloride with 1 part of methyl
alcohol. This mixture should have an absorbance of less than 49.5 Weigh a 0.1231-g sample of the dry trityl ether
0.2 at 259 mm in a 1-cm silica cell measured against air; derivative into a 100-mL volumetric flask fitted with a ground-
otherwise, the solvents should be redistilled. glass stopper, and dissolve in the methylene chloride-methyl
alcohol mixture. Dilute to 100 mL and mix thoroughly.
48.4 Pyridine, redistilled to a water content less than Measure the absorbance of this solution in a 1-cm silica cell
0.05 %. The water content may be reduced further by storing using a spectrophotometer at 259 nm against the solvent as a
over a suitable drying agent, such as a molecular sieve, Type reference.
4A.
48.5 Trityl Chloride (Chlorotriphenylmethane or Triphenyl- 50. Calculation
methyl Chloride).
50.1 Calculate the trityl content, t, for this concentration of
0.1 g/100 g and with a correction of 0.015 for the absorbance
6
of the cellulose acetate as follows:7
Malm, C. J., Tanghe, L. J., Laird, B. C., and Smith, G. D., “Determination of
Total and Primary Hydroxyl in Cellulose Esters by Ultraviolet Absorption Trityl, % 5 25.25~ A 2 0.015! (23)
Methods,” Analytical Chemistry, ANCHA, Vol 26, 1954, p. 189.
7
Malm, C. J., Tanghe, L. J., and Laird, B. C., “Primary Hydroxyl Groups in where:
Hydrolyzed Cellulose Acetate,” Journal of the American Chemical Society, JACSA,
A = absorbance.
Vol 72, 1950, p. 2674.

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 D817 − 12
50.2 Calculate the weight percentage of primary hydroxyl 54.7 Nitric Acid-Perchloric Acid Mixture—Mix 5 volumes
as follows: of concentrated HNO3 with 1 volume of concentrated perchlo-
Primary hydroxyl, % 5 7.02 t/ ~ 100.4 2 t ! (24) ric acid (HClO4, 70 %).
50.3 Calculate the percentage primary hydroxyl of the total 54.8 Phenolphthalein Indicator Solution (1 g/100 ml)—
hydroxyl as follows: Dissolve 1 g of phenolphthalein in 100 mL of ethyl alcohol
(95 %).
Primary hydroxyl of total hydroxyl, % 5 ~ B/C ! 3 100 (25)
54.9 Silver Nitrate Solution (50 g/L)—Dissolve 50 g of
where: silver nitrate (AgNO3) in water and dilute to 1 L.
B = value of primary hydroxyl as determined in 50.2, and
54.10 Sodium Carbonate—(Na2CO3).
C = value of total hydroxyl as determined in 44.2.
54.11 Sodium Hydroxide Solution (400 g/L)—Dissolve 400
SULFUR OR SULFATE CONTENT g of sodium hydroxide (NaOH) in water and dilute to 1 L.

51. Summary of Test Method 55. Procedure

51.1 The sulfur or sulfate content of cellulose acetate is
Treatment Prior to Analysis
measured by oxidizing the sample in a nitric acid-perchloric
acid mixture and determined gravimetrically as barium sulfate. 55.1 Remove uncombined sulfur as follows (Note 11):
To determine combined sulfur the sample must first be repre- Dissolve 25 g of sample in approximately 300 mL of acetone,
cipitated into dilute acid to remove noncombined sulfur com- depending on the viscosity. If the sample is of too high acetyl
pounds. content to be directly soluble in acetone, cool in a dry ice
cabinet overnight; then allow to come to room temperature
51.2 The sulfur or sulfate content may also be determined while tumbling or stirring. Filter the solution, if necessary,
by Test Method D2929, The X-ray method shall be calibrated through felt or a coarse sintered-glass crucible. Precipitate with
against the chemical method following in Sections 53 to 54, rapid stirring into a beaker or pail containing 2 to 3 L of acetic
and the sample shall be treated in accordance with 53.1, if acid (1 + 49). Filter through a cloth bag or a Büchner funnel
combined sulfur is to be determined. and give two 15-min washes with water using mechanical
agitation. A little Na2CO3 may be added to the last wash to
52. Significance and Use stabilize samples of high sulfur content. Filter and dry over-
52.1 Sulfur and sulfate content indicates the amount of night at 60°C.
sulfur in the cellulose ester either as inorganic salts (usually
NOTE 11—To analyze for total sulfur content omit this treatment.
sulfates) or as organic sulfate (usually as sulfate ester com-
bined to the cellulose backbone). The presence of high levels of Decomposition
sulfur and sulfate can be detrimental to the melt stability of the
55.2 Weigh 10 6 0.1 g of cellulose acetate and transfer to a
ester.
clean wide-mouth, 500-mL Erlenmeyer flask. Add 50 mL of
the HNO3–HClO4 mixture to the flask, and swirl the flask
53. Apparatus gently to wet the sample thoroughly. Place the modified funnel
53.1 Funnel, modified by cutting the stem off at the apex of in the mouth of the flask and heat the flask carefully on a hot
the funnel and fire polishing. plate in a fume hood. (Warning—Use the utmost care in
53.2 Crucibles, 30-mL, extra-fine porosity. handling the HNO3–HClO4 mixture. If a spill occurs, wash
down with plenty of water. Wear safety glasses or a face
53.3 Oven, controlled at 120 to 125°C. shield.)
53.4 Muffle Furnace, controlled at 800 6 50°C. 55.3 After the mixture becomes hot and less viscous,
increase the heat of the hot plate. Continue the digestion until
54. Reagents all the sample has been oxidized and the thick reddish-brown
54.1 Acetone. fumes of nitric oxide have been expelled. At this point, white
fumes will appear and a rather vigorous reaction will occur that
54.2 Acetic Acid (1 + 49)—Mix 1 volume of glacial acetic is caused by the last traces of organic material being oxidized
acid with 49 volumes of water. and the nitric acid fuming off.
54.3 Barium Chloride Solution (100 g/L)—Dissolve 100 g 55.4 When this reaction starts, remove the flask from the hot
of barium chloride (BaCl2·2H2O) in water and dilute to 1 L. plate, swirl gently for a few seconds, and set it on the shelf in
54.4 Hydrochloric Acid (1 + 1)—Mix 1 volume of concen- front of the hood until the reaction is complete. Place the flask
trated hydrochloric acid (sp gr 1.19) with 1 volume of water. back on the hot plate and continue the digestion until the
HClO4 refluxes about half way up the side of the Erlenmeyer
54.5 Nitric Acid (sp gr 1.42)—Concentrated nitric acid flask and about 5 mL is left in the flask. The HNO3–HClO4
(HNO3). mixture should be clear and colorless. If it is not, set the flask
54.6 Nitric Acid (2 + 3)—Mix 2 volumes of concentrated off the hot plate to cool and then add 3 to 5 mL of HNO3 (sp
nitric acid (sp gr 1.42) with 3 volumes of water. gr 1.42). Replace the flask on the hot plate and continue heating

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 D817 − 12
until the HClO4 refluxes half way up the flask. Remove the 55.11 From time to time, and especially when using new
flask from the hot plate and allow the flask and its contents to reagents, run a blank in duplicate in the reagents. If the weight
cool. of the precipitate exceeds 0.0005 g, investigate and eliminate
the cause. This is equivalent to an error of 0.002 % on a 10-g
Determination of Barium Sulfate sample.
55.5 Wash the modified funnel top thoroughly with water,
collecting the rinsings in the flask. Add 50 mL of water. Swirl 56. Calculation
the flask to mix the solution thoroughly. Add 2 drops of
56.1 Calculate the percentage of sulfur and sulfate as
phenolphthalein indicator solution and neutralize the acid with
follows:
the NaOH solution to a faint pink. Acidify immediately with
HCl (1 + 1), dropwise, until the solution is just acid to Sulfur, % 5 $ @ ~ C 2 B ! 2 ~ E 2 D ! # 3 0.1374/A % 3 100 (26)
phenolphthalein; then add 2 mL of HCl (1 + 1). Sulfate, % 5 $ @ ~ C 2 B ! 2 ~ E 2 D ! # 3 0.4115/A % 3 100 (27)
55.6 Filter through a 12.5-cm fine-porosity paper into a where:
clean 400-mL beaker. Wash the flask thoroughly with water, A = weight of sample, g,
filtering the washings through the paper. Finally wash the paper B = weight of crucible for sample, g,
thoroughly with ten portions of hot water. Dilute the filtrate to C = weight of crucible and BaSO4 for sample, g,
approximately 200 mL. Place the beaker on the hot plate and C−B = weight of BaSO4 for sample, g,
heat almost to boiling. Slowly add 10 mL of BaCl2 solution D = weight of crucible for blank, g,
from a pipet, stirring the solution during the addition. Do not E = weight of crucible and BaSO4 for blank, g, and
add the BaCl2 solution rapidly, as from a graduate, since the E−D = weight of BaSO4 for blank, g.
rapid addition will produce an impure precipitate. Remove the
stirring rod from the beaker and wash it with a stream of water HEAT STABILITY
from the wash bottle, collecting the washings in the beaker.
Cover the beaker with a watch glass and keep the mixture near 57. Summary of Test Method
the boiling temperature for 6 h or overnight. Do not allow the 57.1 The heat stability of a cellulose ester is one indication
liquid to evaporate to dryness. of its quality. It is measured by heating the sample for a
55.7 Using suction, decant the supernatant liquid through an specified time and temperature, observing it for amount and
extra-fine porosity porcelain filter crucible that has been uniformity of color developed, and possibly also measuring the
previously rinsed with acetone, ignited, and weighed to the loss of viscosity as a result of heating. Suggested times of
nearest 0.1 mg. Transfer the precipitate with the aid of a stream heating are 8 h at 160°C, 8 h at 180°C, or 2 h at 190°C. The
of hot water. Always use a stirring rod in this transfer. Scrub the time and temperature of heating, method of grading, and limits
sides and bottom of the beaker with a rubber policeman to are matters for agreement between the purchaser and the seller.
remove any adhering precipitate. The crucibles may be used to
collect several precipitates one on top of the other. Close 58. Significance and Use
control of temperature and time of heating and cooling are
58.1 The heat stability of a cellulose ester is one indication
necessary. Cleaning with hot water is generally sufficient;
of its quality.
drastic attack with cleaning solution should be avoided.
55.8 Wash the precipitate on the filter until free of chlorides 59. Apparatus
by the following test: To 5 mL of wash water, collected in a
separate test tube or on a watch glass, add 1 mL of HNO3 59.1 Heater Block—A metal block of suitable size heated
(2 + 3) and 1 mL of AgNO3 solution. The appearance of a electrically and maintained at the specified temperature within
milky white precipitate indicates the presence of chlorides, and 61°C. This is best accomplished by providing continuous heat
the washing should therefore continue until the test is negative. to hold the temperature a few degrees below the specified
Do not attempt to get a completely negative test for chloride. temperature, and providing intermittent additional heat ther-
Discontinue washing when no more than a faint opalescence is mostatically controlled. Holes shall be drilled in the top of the
produced in the test. block to hold test tubes, a thermoregulator, and a thermometer.
The block should be insulated.
55.9 Finally pour a few millilitres of pure acetone through
the filter and suck it dry. Place the crucible in a larger crucible 59.2 Test Tubes, either 18 by 150-mm or 20 by 150-mm,
or in a metal tray with perforated sides and bottom for fitted with corks. The corks shall be fitted with glass tubes the
protection and place it in an oven at 120 to 125°C for 1 h. Do length of the cork and 4 mm in inside diameter or shall have a
not handle the crucibles with the fingers between ignition and small V-shaped notch of equivalent cross-section cut in a
the completion of weighing; use forceps. vertical position.
55.10 Remove the crucible from the oven and ignite it for
60. Solvent
10 min in a muffle furnace at 800 6 50°C. Cool in a desiccator
for 75 6 15 min and weigh to the nearest 0.0001 g. It is 60.1 Methylene Chloride-Methyl Alcohol Mixture—Mix 9
permissible to return the crucible to the oven for at least 15 min parts by weight of methylene chloride with 1 part of methyl
before transferring to the desiccator. alcohol.

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64. Solution Color by Spectrophotometer
64.1 The color of the solution prepared as described in
Section 63 may also be measured spectrophotometrically.
Measure the absorbance at 400 nm against the solvent, using a
suitable spectrophotometer with a 1-cm silica cell.

65. Viscosity Change

65.1 Measure the limiting viscosity number of the heated
sample and of an unheated sample as described in Sections 67
to 71 of this test method. The percentage loss of viscosity as the
result of heating is a measure of heat stability.

66. Precision and Bias

66.1 No statement on bias can be made as no reference
material is available as a standard.
LIMITING VISCOSITY NUMBER

67. Summary of Test Method

67.1 Limiting viscosity number, expressed in millilitres of
solution per gram of solute, is determined by measuring the
FIG. 3 Wagner Capillary Tube Viscometer9
flow times of a solution of known concentration and also of the
solvent used and making a calculation by means of the
modified Baker-Philippoff equation.
67.2 Intrinsic viscosity, expressed in decilitres per gram of
61. Heat Treatment solute, is determined in the same way by expressing c in grams
per 100 mL in 71.2. Limiting viscosity number is thus
61.1 Place the sample, ground to pass a No. 20 (841-µm)
100 × intrinsic viscosity.
sieve, in a clean, dry test tube and pack it firmly and uniformly.
Stopper with a cork having a notch or tube as described in 59.2. 68. Significance and Use
Heat the tube and contents for 8 h at 180°C or as otherwise
specified. 68.1 Limiting viscosity number can be used to estimate the
molecular weight of a cellulose ester by using the Mark-
62. Dry Color Evaluation Houwink equation and constants measured for the solvent,
temperature, and ester of concern.
62.1 Examine the heated sample for uniformity of color and
for the presence of charred or decomposed spots. Compare the 69. Apparatus
color of the material at the bottom of the tube with standards 69.1 Capillary Viscometer, such as the Wagner apparatus
prepared as follows: Heat portions of a check batch of similar (see Fig. 3)8 or an Ostwald-Fenske-Cannon pipet, that will give
particle size, representative quality and stability, and accepted a flow time for the solvent of not less than 70 s.
by mutual agreement between the purchaser and the seller.
Pack portions of this check batch firmly in each of twelve 69.2 Water Bath—A constant-temperature water bath con-
clean, dry test tubes and stopper with corks as described in trolled at 25.0 6 0.1°C and with a pump for circulating the
59.2. Heat the tubes at 180°C, or as otherwise specified, water through the viscometer jacket or tank.
remove one tube each 2 h, and mark the time of heating in 69.3 Stop Clock or Watch, calibrated in 1⁄10 s.
hours on each tube. This set of numbered tubes serves as the
color standards. They should be checked and renewed if 70. Procedure
necessary every 6 months. 70.1 Sample Preparation—Dry about 0.26 g of sample in a
weighing bottle at 105 6 3°C for 2 h, stopper, and cool in a
63. Solution Color Using Platinum–Cobalt Standards desiccator. Weigh the bottle containing the sample to the
63.1 Heat a 1-g sample for the specified time and tempera- nearest 0.001 g, transfer the sample to a 250-mL flask, and
ture and, after cooling, examine for charred or decomposed reweigh the bottle. Pipet into the flask 100 mL of solvent at 25
spots. Dissolve the heated sample in 15 mL of the methylene 6 0.1°C. The solvent used should be mutually agreed upon by
chloride–methyl alcohol mixture. Compare the color of the the purchaser and the seller. Suitable solvents are listed in
solution (viewing transversely) with test tubes of platinum- Table 1. After the sample is completely dissolved, place it in
cobalt color standards, prepared as described in Section 80. (It
may be necessary to prepare standards having as much as 2000 8
Wagner, R. H., and Russell, John, “Capillary Tube Viscometer for Routine
ppm of platinum for this purpose or to dilute the sample Measurement of Dilute High Polymer Solutions,” Analytical Chemistry, Vol 20,
solution before grading.) 1948, pp. 151–7.

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 D817 − 12
TABLE 1 Solvents for Limiting Viscosity Number Determination 71.2 Calculate the limiting viscosity number, [η], as fol-
Value of lows:
Ingredients, % k for Cal-
SolventA @ η # 5 ~ k/c ! @ antilog ~~ logη/η 0 ! /k ! 2 1 # (31)
by weight culation
(71.2)
A 90 % acetoneB 10
where:
10 % ethyl alcoholC k = values from Table 1 (Note 13), and
B acetoneB 10
C or D 90 % methylene chlorideD 3
c = concentration in g/mL.
10 % ethyl alcoholC NOTE 13—Different values may be used by agreement between the
E 96 % acetoneB 10 purchaser and the seller.
4 % water
F 90 % methylene chlorideD 3 71.3 Calculate intrinsic viscosity, η, in accordance with
10 % methanolE 71.2, but express c in grams per 100 mL.
A
Solvent designations conform to those used in Table 2 for viscosity
determinations.
B
72. Precision and Bias
Acetone (99.4 ± 0.1 %) containing 0.3 to 0.5 % water and under 0.3 % ethyl
alcohol. 72.1 No statement on bias can be made as no reference
C
Ethyl alcohol (95 % by volume). Formula 2B or 3A denatured ethyl alcohol may material is available as a standard.
be used.
D
Methylene chloride having a boiling range of 39.2 to 40.0°C and less than
0.001 % acidity calculated as HCl. VISCOSITY
E
Methyl alcohol (sp gr 20/20°C = 0.785 to 0.795).
73. Significance and Use
73.1 A measurement of viscosity is of great practical utility
in determining the proper processing equipment and process
the constant-temperature bath at 25°C along with a portion of concentrations for cellulose esters.
the solvent used, and allow sufficient time for both to come to
74. Procedure
temperature before making the viscosity measurements. Dur-
ing this conditioning period, water at 25°C should be circulat- 74.1 Solution—Dry the sample for 1 to 2 h at 105 6 3°C and
ing through the water jacket of the viscometer to allow ample cool in a desiccator. Prepare a solution of the dried sample in
time for the pipet to reach temperature equilibrium. a solvent and at a concentration mutually agreed upon by the
purchaser and the seller. Suitable solutions are listed in Table 2.
70.2 Viscosity Measurements—Rinse the reservoir and the
outside of the capillary tube thoroughly with solvent. Rinse the 74.2 Viscosity Determination—Prepare the solution and
inside of the capillary tube twice by alternately applying measure the viscosity in accordance with Test Method D1343,
pressure at points Band A(see Fig. 3). Discard the wash portion (see Note 16 in Section 81).
of the solvent. Pour more solvent into the reservoir and allow
75. Report
several minutes for complete drainage and thermal equilibrium
to be obtained. Adjust the outer meniscus to a reference point, 75.1 Report the results in poises, unless otherwise specified.
D, that will give a flow time between 70 and 100 s. Apply air The viscosity value shall be prefixed with the letter A, B, C,
pressure at B to force the solvent up through the capillary past etc., corresponding to the formula of the solution employed.
the upper timing mark, C, on the measuring bulb, E. Record the
time in seconds required for the meniscus to fall between the TABLE 2 Solutions for Viscosity Determination
timing marks, C and F. Take a minimum of two readings. Formula
Repeat these operations, substituting the solution for the A B C D E F
solvent. Ingredients, Weight %
Cellulose ester 20A 20A 20B 15C 20A 10C
71. Calculation AcetoneD 72 80 ... ... ... ...
Acetone, 96 percent ... ... ... ... 80 ...
71.1 Calculate the viscosity ratio, η/η0 as follows: Water, 4 percent
Ethyl alcoholE 8 ... 8 8.5 ... ...
Viscosity ratio 5 t 1 /t 2 (28) Methyl alcoholF ... ... ... ... ... 9
Methylene chlorideG ... ... 72 76.5 ... 81
where: Typical Solution Densities, g/mL at 25°C
0.85 0.86 1.25 1.23 0.86 1.24
t1 = efflux time of solution, and
A
t2 = efflux time of solvent. Suitable for most mixed esters having less than about 40 % acetyl and more than
about 8 % propionyl or butyryl.
NOTE 12—Strictly, the viscosity ratio is defined as η/η0 where η and η0 B
Suitable for most of the commercial cellulose acetate propionates and acetate
are the viscosities of the solution and solvent, respectively, and are related butyrates.
to the corresponding efflux times by: C
Suitable for most of the commercial cellulose acetate propionates and acetate
butyrates. Particularly good for esters containing more than 40 % acetyl.
η 5 Ct 2 Eρ/t 2 (29) D
Acetone (99.4 ± 0.1 %) containing 0.3 to 0.5 % water and under 0.3 % ethyl
η 0 5 Ct0 2 Eρ 0 /t 0 2 (30) alcohol.
E
Ethyl alcohol (95 % by Vol). Formula 2B, 3A, or 30 denatured ethyl alcohol may
where: be used.
C and E are constants for the particular viscometer used. F
Methyl alcohol (sp gr 20/20C = 0.785 to 0.795).
The equation in 71.1 follows if the second term in these relations, a kinetic G
Methylene chloride having a boiling range of 39.2 to 40.0°C and less than
energy correction, is negligible and the respective solvent and solution 0.001 % acidity calculated as HCl.
densities, ρ0 and ρ, are substantially equal.

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76. Precision and Bias NOTE 14—These bottles may also be used for determination of
viscosity, as described in 74.2.
76.1 No statement on bias can be made as no reference
material is available as a standard. 79.3 Cap Liners—Cap liners shall be of a composition not
affected by the solvents used. Liners of fiber board covered
COLOR AND HAZE with cellophane or aluminum foil are usually satisfactory, but
vinyl resin or waxed liners may cause interference with
77. Summary of Test Method viscosity, color, or haze measurements.
77.1 Color and haze determinations on cellulose ester solu-
tions are made by comparison with standards. Simultaneous 80. Reference Standards
measurement of these properties is desirable because haze 80.1 Color Standards—A color standard containing 500
reduces the amount of color observed. ppm of platinum may be purchased or the solution may also be
prepared as follows: Dissolve 1.245 g of potassium platinum
78. Significance and Use chloride (K2PtCl6), containing 0.500 g of platinum, and 1.000
78.1 Solution color and haze of a cellulose ester is a g of crystallized cobalt chloride (CoCl2·6H2O), containing
measurement of the optical properties of cellulose esters when 0.248 g of cobalt, in water, add 100 mL of HCl (sp gr 1.19), and
dissolved in a specific solvent. dilute to 1 L with water. Prepare standards containing 50, 60,
70, 80, 90, 100, 125, 150, 175, 200, 250, 300, 350, 400 and 500
79. Apparatus ppm of platinum by diluting suitable aliquots of the standard
79.1 Light Box—A suitable light box (Fig. 4) is described as solution to 500 mL with water. Place these standards in the
follows: The light source consists of a mercury vapor bulb special bottles (see 79.2), taking care to select bottles with
which requires an autotransformer for the current source. The good clarity and free of flaws. Label and cap tightly.
bulb is mounted horizontally across the lower front part of a 80.2 Haze Standards—Prepare haze standards by diluting a
plywood box 356 mm (14 in.) wide, 430 mm (17 in.) high, and stock solution having a turbidity of 1000 ppm. Prepare bottles
330 mm (13 in.) deep. This box is lined with a heat resistant containing 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 125, 150,
board and is painted black inside, except that the inside back 175, 200, and 400 ppm of turbidity, label, and cap tightly.
surface toward the viewer is white. A bottle holder large
enough to hold four bottles is built onto the front of the light NOTE 15—The previously recommended stock solution for preparing
these standards was made from fuller’s earth, water, and hydrochloric
box, and a 64 by 150-mm (21⁄2 by 6-in) horizontal viewing hole acid. This solution is no longer available. A comparable stock solution can
is cut through the front of the box. This opening is covered with be made using diatomaceous earth. To obtain haze levels equivalent to the
clear glass, and a 6-mm (1⁄4-in.) strip of black tape is fastened fuller’s earth standard, 1.1 parts of diatomaceous should be used in place
to the glass horizontally to aid in judging haze in the solution. of 1.0 parts of fuller’s earth in preparing the aqueous suspension. No
Holes are cut in the bottom and top of the box for cooling by hydrochloric acid is needed.
air convection. For continuous use, forced circulation of air
would be desirable. A black metal baffle over the bulb prevents 81. Procedure
direct light on the viewing glass. 81.1 Prepare the solution to be graded by dissolving the
79.2 Sample Bottles—The bottles used for the sample solu- cellulose ester in the specified amount and kind of solvent, in
tions are French square bottles, 470-mL (16-oz), with screw one of the square bottles. See Table 2 for suitable solutions. At
caps. These same bottles may be used for the color and haze least 350 mL are required. Tumble until a uniform solution is
standards. obtained. Allow the solution to stand until it is free of bubbles
before grading it for color and haze.
81.2 Place the bottle containing the solution to be graded at
the front of the shelf on the apparatus and place a similar bottle
containing water behind it. Place the freshly shaken haze
standard at the front of the shelf beside the bottle containing the
solution to be tested and place the color standard behind it.
Determine the amount of color and haze in the solution by
changing the color and haze standards until as good a match as
possible has been obtained. The haze standards settle out
quickly so they must be reshaken at short intervals. Report
results in parts per million for both color and haze.
NOTE 16—When viscosity, color, and haze determinations, and an
observation of general appearance are to be made on a cellulose ester
sample, a considerable saving in time can be made by using one solution
in a square bottle for all three determinations. Dry the cellulose ester as
required for the viscosity determination, prepare the solution carefully,
and allow the bottle to stand long enough to form a thick solution before
tumbling, to avoid solvent loss around the cap. Use a large enough sample
to provide at least 350 mL of solution in the bottle. Measure the viscosity
FIG. 4 Color and Haze Apparatus as described in Test Method D1343.

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 D817 − 12
82. Precision and Bias
82.1 No statement on bias can be made as no reference
material is available as a standard.
83. Keywords
83.1 apparent acetyl; ash; cellulose acetate butyrate; cellu-
lose acetate propionate; cellulose esters; color; free acidity;
haze; hydroxyl; limiting; partition; sulfate content; viscosity

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