Designation: D 871 – 96

AMERICAN SOCIETY FOR TESTING AND MATERIALS

100 Barr Harbor Dr., West Conshohocken, PA 19428
Reprinted from the Annual Book of ASTM Standards. Copyright ASTM

Standard Test Methods of Testing

Cellulose Acetate1
This standard is issued under the fixed designation D 871; 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 specifications are available.4 Other grades may be used, pro-

1.1 These test methods cover procedures for testing cellu- vided it is first ascertained that the reagent is of sufficiently
lose acetate. high purity to permit its use without lessening the accuracy of
1.2 The test procedures appear in the following sections: the determination.
Sections
3.2 Unless otherwise indicated, references to water shall be
Ash 8 to 11 understood to mean reagent tared, low, wide-form weighing
Color and Haze 67 to 72 bottle and water, conforming to Specification D 1193.
Combined Acetyl or Acetic Acid Content
Test Method A. Solution Method 17, 19 to 23
Test Method B. Heterogeneous Saponification Method 17, 24 to 26
MOISTURE CONTENT
Free Acidity 12 to 16
Heat Stability 47 to 56 4. Significance and Use
Hydroxyl Content 27 to 33
Intrinsic Viscosity 57 to 62
4.1 Moisture content of the cellulose ester can be used to
Moisture Content 4 to 7 estimate the dry weight of the cellulose ester. Since cellulose
Primary Hydroxyl Content 34 to 39 esters are desiccants, their moisture content can vary greatly
Sulfur or Sulfate Content 40 to 45
Viscosity 63 to 66
depending on storage.

This standard does not purport to address the safety con- 5. Procedure
cerns, if any, associated with its use. It is the responsibility of 5.1 Transfer about 5 g of the sample to a tared, low,
the user of this standard to establish appropriate safety and wide-form weighing bottle and weigh to the nearest 0.001 g.
health practices and determine the applicability of regulatory Dry in an oven for 2 h at 105 6 3 C. Remove the bottle from
limitations prior to use. the oven, cover, cool in a desiccator, and weigh.
2. Referenced Documents 6. Calculation
2.1 ASTM Standards: 6.1 Calculate the percentage of moisture as follows:
D 1193 Specification for Reagent Water2
Moisture, % 5 ~A/B! 3 100
D 1343 Test Method for Viscosity of Cellulose Derivatives
by Ball-Drop Method3 where:
D 2929 Test Method for Sulfur Content of Cellulosic Ma- A 5 weight loss on heating, g, and
terials by X-Ray Fluorescence3 B 5 sample used, g.
D 5897 Test Method for Determination of Percent Hydroxyl
on Cellulose Esters by Potentiometric Titration— 7. Precision and Bias
Alternative Method3 7.1 No statement on bias can be made as no reference
material is available as a standard.
3. Purity of Reagents
3.1 Reagent grade chemicals shall be used in all tests. ASH
Unless otherwise indicated, it is intended that all reagents shall 8. Significance and Use
conform to the specifications of the Committee on Analytical
Reagents of the American Chemical Society, where such 8.1 Ash content gives an estimate of the inorganic content
of cellulose ester samples. The presence of high levels of
inorganic content (ash) can be detrimental to the melt stability

1
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 4
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 871 – 46. Last previous edition D871 – 91. Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
2
Annual Book of ASTM Standards, Vol 11.01. and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
3
Annual Book of ASTM Standards, Vol 06.03. MD.

1
 D 871
and optical clarity of a cellulose ester in melt processing or act 15. Calculation
as a potential source of insolubles when the ester is used in 15.1 Calculate the percentage of acidity as free acetic acid
solution. as follows:
9. Procedure Free acetic acid, % 5 @~A 2 B!N 3 0.06 3 100#/W (1)
9.1 Dry the sample for 2 h at 105 6 3°C and weigh 10 to 50 where:
g, to the nearest 0.01 to 0.1 g, depending on its ash content and A 5 NaOH solution used to titrate the sample, mL,
the accuracy desired. An air-dried sample may be used and B 5 NaOH solution used to titrate the blank, mL,
calculated to dry weight using the value for moisture deter- N 5 normality of the NaOH solution, and
mined as in Sections 5 and 6. Burn directly over a flame in a W 5 sample used, g.
100-mL tared platinum crucible that has been heated to
constant weight and weighed to the nearest 0.1 mg. Add the 16. Precision and Bias
sample in portions if more than 10 g is taken. The sample 16.1 No statement on bias can be made as no reference
should burn gently and the portions should be added as the material is available as a standard.
flame subsides. Continue heating with a burner only as long as
the residue burns with a flame. Transfer the crucible to a muffle COMBINED ACETYL OR ACETIC ACID
furnace and heat at 550 to 600°C for 3 h, or longer if required, CONTENT
to burn all the carbon. Allow the crucible to cool and then
transfer it, while still warm, to a desiccator. When the crucible 17. Scope
has cooled to room temperature, weigh accurately to the 17.1 Two test methods are described for determining the
nearest 0.1 mg. combined acetyl or acetic acid content. The first, described in
Sections 19 to 22, is more precise, but less widely applicable,
10. Calculation than the method described in Sections 24 to 26.
10.1 Calculate the percentage of ash as follows:
Ash, % 5 ~A/B! 3 100
18. Significance and Use
18.1 Acetyl or acetic acid content is a measure of the
where: amount of acetic acid esterified onto the cellulose backbone of
A 5 ash, g, and the polymer. The amount of substitution of acetate ester has a
B 5 sample used, g. very strong effect on the polymer’s solubility and physical
11. Precision and Bias properties.
11.1 No statement on bias can be made as no reference Test Method A—Solution Method
material is available as a standard.
19. Apparatus
FREE ACIDITY
19.1 Weighing Bottle, glass-stoppered, 15-mL capacity,
12. Significance and Use 25-mm diameter by 50-mm high.
12.1 Free Acidity is a measure of unesterified organic acid 19.2 Tray, copper or aluminum, approximately 5 3⁄8 in.
in the ester. The presence of high levels of free acid is (136.5 mm) square, containing 25 compartments 1 in. (25.4
potentially detrimental to the melt processing of the ester and mm) square. Each compartment shall have the correct dimen-
can impact the odor of the ester. sions to contain one weighing bottle. The entire tray shall fit
inside a desiccator and should have a basket-type handle to
13. Reagents facilitate the introduction and removal of the tray (convenient
13.1 Phenolphthalein Indicator Solution (1 g/100 mL)— but not essential).
Dissolve 1 g of phenolphthalein in 100 mL of ethyl alcohol 19.3 Buret, automatic zero, 35-mL, 25-mL bulb, stem
(95 %). graduated from 25 to 35 mL in 0.05-ml increments; or pipet,
13.2 Sodium Hydroxide, Standard Solution (0.01 N)— automatic zero, 30-mL, for 1.0 N NaOH solution.
Prepare and standardize a 0.01 N solution of sodium hydroxide 19.4 Buret, automatic zero, 15-mL, 10-mL bulb, stem
(NaOH). graduated from 10 to 15 mL in 0.05-mL increments, for 1 N
H2SO4.
14. Procedure 19.5 Buret, 5-ml, in 0.01 or 0.1-mL divisions, for back
14.1 Shake 5 g of the sample, ground to pass a No. 20 (850 titration with 0.1 N NaOH solution.
µm) sieve and corrected for moisture content if necessary, in a 19.6 Magnetic Stirrer, for single flask.
250-mL Erlenmeyer flask with 150 mL of freshly boiled, cold 19.7 Magnetic Stirrer, capacity twelve or more flasks.
water. Stopper the flask and allow it to stand for 3 h. Filter off 19.8 Stirring Bars, stainless steel Type 416, length 50 mm,
the cellulose acetate and wash it with water. Titrate the diameter 5 to 6 mm, or equivalent, dimensions not critical.
combined filtrate and washings with 0.01 N NaOH solution,
using phenolphthalein indicator solution. 20. Reagents
14.2 Run a blank determination on the water, using the same 20.1 Acetone—Add one 30-mL portion of 1.0 N NaOH
volume as was used in extracting the sample. solution to a mixture of 150 mL acetone and 100 mL hot water,

2
 D 871
allow to stand with frequent swirling for 30 min, and titrate is not available, spread the sample in a thin layer over the
with 1.0 N H2SO4. Add another 30-mL portion of 1.0 N NaOH bottom of the flask, add 15 mL of acetone, swirl to wet the
solution to 100 mL of hot water, allow to stand for 30 min, and particles with acetone, stopper the flask, and allow the mixture
titrate. The difference between the two titrations shall not to stand undisturbed for 20 min. Add 75 mL of pyridine
exceed 0.05 mL. without shaking or swirling, and allow to stand for 10 min.
20.2 Dimethyl Sulfoxide. Heat the solution just to boiling and swirl or stir for 5 min.
20.3 Pyridine. Again heat to boiling and swirl or stir for 10 min. Continue to
20.4 Sodium Hydroxide Solution (40 g/L)—Dissolve 40 g of heat and stir until the mixture is homogeneous and all large gel
sodium hydroxide (NaOH) in water and dilute to 1 L. masses are broken down into individual highly swollen par-
20.5 Sodium Hydroxide, Standard Solution (0.1 N)— ticles. When these highly swollen gel particles are well
Prepare and standardize a 0.1 N solution of NaOH. dispersed and are not fused together in large gel masses, no
20.6 Sulfuric Acid (1.0 N)—Prepare and standardize a 1.0 further heating is necessary. Cool the flask, add 30 mL of
N solution of sulfuric acid (H2SO4). acetone, and swirl or stir for 5 min. Proceed in accordance with
20.7 Phenolphthalein Indicator Solution (1 g/100 mL)— 21.4.
Dissolve 1 g of phenolphthalein in 100 ml of ethyl alcohol 21.4 Add 30 mL of NaOH solution (40 g/L) with constant
(95 %). swirling or stirring to the solution of the sample and also to the
blank. Use of a magnetic stirrer is recommended (Note 2). It is
21. Procedure absolutely necessary that a finely divided precipitate of regen-
21.1 Dry 1.9 6 0.05 g of the ground well-mixed sample in erated cellulose, free from lumps, be obtained. Stopper the
a weighing bottle for 2 h at 105 6 3°C and weigh the dried flask and let the mixture stand with occasional swirling, or stir
sample by difference to the nearest 1 mg into a 500-mL on the magnetic stirring unit. Allow 30 min for saponification
wide-mouth Erlenmeyer flask. Prepare a blank by drying of lower acetyl samples, 2 h for high acetyl samples when
approximately 3.8 g of potassium acid phthalate and weighing dimethyl sulfoxide is the solvent, and 3 h when pyridine is the
it by difference into a flask as described. Carry the blank solvent. At the end of the saponification period, add 100 mL of
through the entire procedure. hot water, washing down the sides of the flask, and stir for 1 or
NOTE 1—Potassium acid phthalate is used so that the concentration of 2 min. Add 4 or 5 drops of phenolphthalein indicator solution
the NaOH in contact with the solvent in the blank will be approximately and titrate the excess NaOH solution with 1.0 N H2SO4 (Note
the same as that in contact with the sample and so that the titration of the 3). Titrate rapidly with constant swirling or stirring ring until
blank will be approximately the same as the titration of the sample, thus the end point is reached; then add an excess of 0.2 or 0.3 mL
avoiding errors caused by using a different buret for the titration of the of H2SO4. Allow the mixture to stand with occasional stirring
blank and the sample or by refilling the 15-mL buret. If desired, however, or preferably stir on the magnetic stirrer for at least 10 min.
the potassium acid phthalate may be omitted.
Then add 3 drops of phenolphthalein indicator solution to each
21.2 If the acetyl content is 32 to 41 % or the acetic acid flask and titrate the small excess of acid with 0.1 N NaOH
content is 45 to 57 %, put the sample into solution as follows: solution to a persistent phenolphthalein end point. Take ex-
Add 150 mL of acetone and 5 to 10 mL of water and swirl to treme care to locate this end point; after the sample is titrated
mix. Stopper the flask and allow it to stand with occasional to a faint pink end point, swirl the mixture vigorously or place
swirling until solution is complete. Solution may be hastened it for a moment on the magnetic stirrer. If the end point fades
by magnetic stirring or by any suitable mechanical shaking that because of acid soaking from the cellulose, continue the
will provide a gentle rocking type of agitation to avoid addition of 0.1 N NaOH solution until a faint persistent end
splashing the solution on the stopper. It is essential that point remains after vigorous swirling or stirring. Titrate the
complete solution be effected. Proceed in accordance with blank in the same manner as the sample.
21.4.
21.3 If the acetyl content is 41 to 44.8 % or the acetic acid NOTE 2—While the amount of magnetic stirring is somewhat optional,
such stirring during the entire period of the determination is strongly
content is 57 to 62.5 %, dissolve the sample by either of the recommended. Solution is more rapid, titrations are more rapid, and the
following two methods: end point can be approached directly and without a back titration.
21.3.1 Gently rotate the flask by hand to distribute and NOTE 3—It is important to correct all 1.0 N H2SO4 buret readings for
spread the sample in a thin layer over the bottom of the flask. temperature and buret corrections.
Add 70 mL of acetone to the flask and swirl gently until the
sample particles are completely wetted and evenly dispersed. 22. Calculation
Stopper the flask and allow it to stand undisturbed for 10 min. 22.1 Calculate the percentage by weight of acetyl and acetic
Carefully add 30 mL of dimethyl sulfoxide from a graduate to acid as follows:
the flask, pouring the solvent down the sides of the flask to
Acetyl or acetic acid, % (2)
wash down any sample particles clinging to the side. Stopper
the flask and allow it to stand with occasional swirling until 5 @~D 2 C!Na 1 ~A 2 B!Nb 1 P# 3 ~F/W! ~Note 4!
solution is complete. Magnetic stirring or gentle mechanical P 5 ~GH 3 1000!/204.2
agitation that will not splash the solution is recommended.
When solution appears to be complete, add 50 mL of acetone where:
A 5 NaOH solution required for titration of the sample,
and swirl or stir for 5 min. Proceed in accordance with 21.4.
mL,
21.3.2 Dimethyl sulfoxide is the preferred solvent, but if it

3
 D 871

B 5 NaOH solution required for titration of the blank, mL, of HCl with 0.5 N NaOH solution to a phenolphthalein end
Nb 5 normality of the NaOH solution, point. Extreme care must be taken to locate this end point.
C 5 H2SO4 required for titration of the sample, mL, After the sample is titrated to a faint pink end point, stopper the
D 5 H2SO4 required for titration of the blank, mL, flask and shake vigorously. The end point may fade because of
Na 5 normality the H2SO4, acid diffusing from the cellulose. Continue the addition of 0.5
F 5 4.305 for acetyl and 6.005 for acetic acid, N NaOH solution and shaking until the faint pink end point
P 5 milliequivalents of potassium acid phthalate, persists after vigorous shaking of the flask.
G 5 potassium acid phthalate used, g,
H 5 purity factor for potassium acid phthalate, and 26. Calculation
W 5 sample used, g.
26.1 Calculate the percentage of combined acetyl or acetic
NOTE 4—When equal volumes of alkali or acid are added to samples acid as follows:
and blank, these amounts cancel out. Thus only the amounts of each added
acetyl or acetic acid, % 5 @~D 2 C!Na 1 ~A 2 B!Nb# 3 ~F/W! (3)
in the titration enter into the calculations. Use of potassium acid phthalate
in the blank is recommended. When it is not used, the term P drops out of
where:
the equation.
A 5 NaOH solution required for titration of the sample,
23. Precision and Bias mL,
B 5 NaOH solution required for titration of the blank, mL,
23.1 No statement on bias can be made as no reference Nb 5 normality of the NaOH solution,
material is available as a standard. C 5 HCl required for titration of the sample, mL,
Test Method B—Heterogeneous D 5 HCl required for titration of the blank, mL,
Saponification Method Na 5 normality of the HCl solution,
F 5 4.305 for acetyl or 6.005 for acetic acid, and
24. Reagents W 5 sample used, g.
24.1 Ethyl Alcohol (75 Volume %)—Mix 790 mL of For- HYDROXYL CONTENT
mula 2B, 3A, or 30 denatured ethyl alcohol and 210 mL of
water. 27. Scope
24.2 Hydrochloric Acid (0.5 N)—Prepare and standardize a
27.1 This test method is applicable to pyridine-soluble
0.5 N solution of hydrochloric acid (HCl).
cellulose esters and is especially useful when the hydroxyl
24.3 Sodium Hydroxide, Standard Solution (0.5 N)—
content is low. Samples containing plasticizer may be analyzed
Prepare and standardize a 0.5 N solution of sodium hydroxide
directly by this test method because the plasticizer is removed
(NaOH).
during washing of the carbanilate.
25. Procedure 27.2 A preferred method is available in Test Method
25.1 Grind the sample in a Wiley mill or other suitable D 5897.
grinder so that 100 % will pass a No. 20 (850-µm). (Grinding
28. Summary of Test Method
may be omitted if the sample has suitable texture.) Dry about
1 g of the sample in a weighing bottle at 105 6 3°C for 2 h, 28.1 Hydroxyl in cellulose acetate is determined by reaction
stopper, and cool in a desiccator. (An oven with mechanical with phenyl isocyanate in pyridine solution under anhydrous
circulation is to be preferred over a convection-type oven). conditions to form the carbanilate derivative. The derivative is
25.2 Weigh the bottle containing the sample to the nearest then analyzed for its carbanilate content by ultraviolet absorp-
0.001 g, transfer the sample to a 250-mL Erlenmeyer flask, and tion.
weigh the bottle again to the nearest 0.001 g. Handle the bottle 28.2 The acetyl content of cellulose acetates may be calcu-
with either tongs or a clean dry cloth during these manipula- lated provided that the degree of polymerization is not exces-
tions. Add 40 mL of ethyl alcohol (75 %) to each sample. sively low.
Include a blank determination with each set of samples and
carry the blank determination through the complete procedure, 29. Significance and Use
including the back titration. 29.1 Hydroxyl content is a measure of the free hydroxyl on
25.3 Heat the flasks, loosely stoppered, for 30 min at 50 to the cellulose backbone of the polymer. Hydroxyl content has a
60°C. Add 40 mL of 0.5 N NaOH solution to each flask and strong effect on the polymer’s solubility and physical proper-
heat again at 50 to 60°C for 15 min. Stopper the flasks tightly ties. Hydroxyl content also impacts the propensity for this
and allow to stand at room temperature for about 48 h. If the polymer to crosslink with various crosslinking agents.
acetyl content of the sample is over 43 %, or if the sample is
hard and horny, allow to stand for about 72 h. At the end of this 30. Apparatus
time back titrate the excess NaOH with 0.5 N HCl, using 30.1 Spectrophotometer, complete with hydrogen light
phenolphthalein as the indicator. Add an excess of about 1 mL source and a set of four 1.00-cm quartz cells, or an equally
of 0.5 N HCl and allow the NaOH to diffuse from the suitable apparatus. The wavelength calibration, as checked
regenerated cellulose for several hours, or, preferably over- against a mercury lamp, shall be within the manufacturer’s
night. The disappearance of the pink color indicates the tolerances. As a further check, measure the absorbance of a
complete neutralization of the NaOH. Titrate the small excess potassium chromate (K2CrO4) solution prepared as follows:

4
 D 871
Dissolve 0.0400 g of K2CrO4 or 0.0303 g of potassium 31. Reagents
dichromate K2Cr2O7 in 0.05 N potassium hydroxide (KOH) 31.1 Acetone.
solution and dilute to 1 litre in a volumetric flask with 0.05 N 31.2 Ethyl Alcohol, denatured, Formula 2B, 3A, or 30.
KOH solution. Using the hydrogen lamp, measure the absor- 31.3 Methylene Chloride-Methyl Alcohol Mixture—Mix 9
bance at 280 nm of a silica cell filled with the K2CrO4 solution parts by weight of methylene chloride with 1 part of methyl
and also of the same cell filled with water. The absorbance of alcohol. This mixture should have an absorbance of less than
the solution minus that of the blank shall be 0.723 6 0.023. 0.2 at 280 nm in a 1.00-cm silica cell measured against air.
30.2 Bottles, 4-oz, with screw caps, for washing the Pure methylene chloride has an absorbance of about 0.05, but
samples. the commercial product may have an absorbance as high as
30.3 Special Reflux Tubes for the carbanilation, constructed 1.00. The methylene chloride and methanol should be selected
as follows (see Fig. 1): Make a test tube approximately 20 by to have low absorbance; otherwise, they should be redistilled.
150 mm from the outer part of a 24/40 standard-taper ground 31.4 Phenyl Isocyanate.
glass joint by closing the open end in a blast lamp. Draw the 31.5 Pyridine, redistilled, low water content, preferably less
tubing on the inner joint to a constriction just above the joint. than 0.05 %.
Cut the glass at that point and seal on a short length of 8-mm
tubing to provide a bearing for a glass stirrer. Make a stirrer of 32. Procedure
4-mm glass rod with a semicircle at right angles to the shaft at
the bottom and small enough to fit into the test tube. When 32.1 In the following procedure the phenyl isocyanate
properly constructed this unit acts as an air condenser, thus reagent shall be used under anhydrous conditions. Therefore,
preventing the loss of solvent by evaporation. the sample, containers, pipet, and all other equipment shall be
30.4 Pipet, serological-type, 5-mL capacity, graduated in thoroughly dried.
0.1-mL divisions. 32.2 Place a 0.5-g sample in a special reflux tube and dry in
30.5 Büchner Funnel, of a size accommodating 90-mm an electric oven at 105°C for 2 h. Remove the tube from the
filter paper. oven, add 5 mL of pyridine, assemble the reflux apparatus
30.6 Automatic Shaker, with speed regulator mechanism. complete with glass stirring rod, and place in the 115 to 120°C
30.7 Electric Oven, maintained at 105 6 3°C. oil bath. Stir occasionally until the sample is completely
30.8 Oil Bath, equipped with a rack to hold several of the dissolved. Add 0.5 mL of phenyl isocyanate, stir thoroughly,
special reflux tubes. This bath shall be kept between 115 and and reflux in the oil bath for 1⁄2 h to complete the reaction. Use
120°C. 0.1 mL of phenyl isocyanate for each percent of estimated
hydroxyl content, but never less than 0.5 mL.
32.3 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. The precipitate should be fluffy and
white. Sticky precipitates indicate too little dilution. Stir the
alcohol vigorously during precipitation. Filter off the precipi-
tate, using paper on a Büchner funnel, with suction applied
only as long as is necessary to remove the bulk of the solvent;
prolonged suction may cause undesirable clumping together of
the precipitate.
32.4 Wash by transferring the precipitate to a 4-oz screw cap
bottle containing 75 mL of ethyl alcohol, capping securely, and
shaking for 1⁄2 h on an automatic shaker at medium speed.
Filter the precipitate on the Büchner funnel, pressing out as
much liquid as possible with a glass stopper. Repeat the
washing and filtering operations twice more. Allow the pre-
cipitate to air-dry 1 to 2 h at room temperature with good
ventilation or preferably overnight to ensure complete removal
of the alcohol. (Samples wet with alcohol may sinter and stick
to paper or glass when dried at 105°C.) Dry the sample at
105°C in the oven for 1 h and cool in a desiccator. Small
manila envelopes are convenient for drying and cooling the
samples.
32.5 Weigh 0.1231 g of the dry precipitate into a 100-mL
FIG. 1 Special Reflux Tube for Carbanilation volumetric flask fitted with a ground-glass stopper. Add 60 to

5
 D 871
80 mL of the methylene chloride-methyl alcohol mixture, and 37.2 Place a 0.5-g sample in the test tube of the special
shake occasionally until complete solution occurs. Dilute to reflux apparatus and dry for 2 h at 105 6 3°C. Add 5 mL of
100 mL and mix thoroughly. Using the spectrophotometer with pyridine, insert the top of the reflux apparatus and the stirrer
a 1-cm silica cell measure the absorbance of the solution at 280 and heat with stirring in a 115 to 120°C oil bath. After the
nm against the solvent mixture as a reference. sample has dissolved, add 0.5 g of trityl chloride. If the total
hydroxyl content exceeds 3 %, use an additional 0.075 g of
33. Calculation trityl chloride for each additional 1 % hydroxyl. Stir the
33.1 Calculate the percentage of carbanilate, c, for a sample mixture thoroughly and reflux in the oil bath for exactly 2 h at
weight of 0.1231 g as follows:5 115 to 120°C. Remove the tube and cool.
Carbanilate, % 5 A 3 17.1 (4) 37.3 Dilute the sample with acetone to the proper viscosity
for precipitation. The amount of acetone used to thin the
where: solution is a critical factor in obtaining a good precipitate.
A 5 absorbance. Samples having low viscosity require little, if any, dilution. The
33.2 Calculate the percentage of hydroxyl as follows: average sample requires the addition of about an equal volume
Hydroxyl, % 5 14.3c/~100 2 c! of acetone. Precipitate the trityl derivative by pouring the
33.3 Calculate the percentage of acetyl as follows: solution into about 200 mL of ethyl alcohol with vigorous
stirring. The precipitate should be fluffy and white. Sticky
Acetyl, % 5 ~4480 2 65.1c! / ~100 2 c! precipitates indicate too little dilution. Separate the precipitate
NOTE 5—The calculation for acetyl content assumes exactly three by filtering through paper on a Büchner funnel, with suction
hydroxyls per anhydroglucose unit and applies to cellulose acetates only. applied only as long as necessary to remove the bulk of the
solvent; prolonged suction may evaporate the alcohol and
PRIMARY HYDROXYL CONTENT cause the precipitate to partially redissolve in the remaining
34. Summary of Test Method pyridine.
37.4 Wash the precipitate by transferring it to a 4-oz screw
34.1 The primary hydroxyl content of cellulose acetate is
cap bottle containing 75 mL of ethyl alcohol, capping securely,
determined by formation of the triphenylmethyl (trityl) ether
and shaking for 1⁄2 h on a shaker at medium speed. Again
and measurement of the trityl group by ultraviolet absorbance.5
collect the precipitate on a Büchner funnel, pressing out as
Trityl chloride reacts preferentially with primary hydroxyls.
much liquid as possible with a glass stopper. Repeat this
Since there is also a slight reaction with secondary hydroxyls,
washing and filtering operation twice more, or until the
standardized reaction conditions are important.6
absorbance of the filtrate at 259 nm is about the same as that of
35. Apparatus an alcohol blank. Allow the precipitate to air-dry on the filter
paper for 1⁄2 h at room temperature with good ventilation, or
35.1 See Section 30.
preferably overnight, to remove most of the alcohol. (Samples
36. Reagents wet with alcohol may sinter or stick to paper or glass when
36.1 Acetone. dried at 105°C.) Transfer the sample to a manila envelope, dry
36.2 Ethyl Alcohol, denatured, Formula 2B, 3A, or 30. it for 1 h at 105°C, and cool in a desiccator.
36.3 Methylene Chloride-Methyl Alcohol Mixture—Mix 9 37.5 Weigh 0.1231 g of the dry trityl ether derivative into a
parts by weight of methylene chloride with 1 part of methyl 100-mL volumetric flask fitted with a ground-glass stopper,
alcohol. This mixture should have an absorbance of less than and dissolve in the methylene chloride-methyl alcohol mixture.
0.2 at 259 nm in a 1-cm silica cell measured against air; Dilute to 100 mL and mix thoroughly. Measure the absorbance
otherwise the solvents should be redistilled. of this solution in a 1-cm silica cell using a spectrophotometer
36.4 Pyridine, redistilled to a water content less than at 259 nm against the solvent as a reference.
0.05 %. The water content may be reduced further by storing 38. Calculation
over a suitable drying agent, such as a molecular sieve, Type
4A. 38.1 Calculate the trityl content, t, for this concentration of
36.5 Trityl Chloride (Chlorotriphenylmethane or Triphenyl- 0.1 g/100 g and with a correction of 0.015 for the absorbance
methyl Chloride), reagent grade. of the cellulose acetate as follows:7
Trityl, % 5 25.25 ~A 2 0.015! (5)
37. Procedure
37.1 The reagents shall be used under anhydrous conditions. where:
It is imperative that the sample and all equipment be thor- A 5 absorbance.
oughly dry. 38.2 Calculate the weight percentage of primary hydroxyl in
cellulose acetate as follows:
Primary hydroxyl, % 5 7.02t / ~100.4 2 t! (6)
5
Malm, C. J., Tanghe, L. J., Laird, B. C., and Smith, G. C., “Determination of
Total and Primary Hydroxyl in Cellulose Esters by Ultraviolet Absorption Meth-
ods,” Analytical Chemistry, ANCHA, Vol 26, 1954, p. 189.
6 7
Malm, C. J., Tanghe, L. J., and Laird, B. C., “Primary Hydroxyl Groups in Wagner, R. H., and Russell, John, “Capillary Tube Viscometer for Routine
Hydrolyzed Cellulose Acetate,” Journal of the American Chemical Society, JACSA, Measurement of Dilute High Polymer Solutions,” Analytical Chemistry, ANCHA,
Vol 72, 1950, p. 2674. Vol 20, 1948, pp. 151–157.

6
 D 871
38.3 Calculate the percentage primary hydroxyl of the total 43.9 Silver Nitrate Solution (50 g/L)—Dissolve 50 g of
hydroxyl as follows: silver nitrate (AgNO3) in water and dilute to 1 L.
Primary hydroxyl of total hydroxyl, % 5 ~B/C! 3 100 (7) 43.10 Sodium Carbonate (Na2CO3).
43.11 Sodium Hydroxide Solution (400 g/L)—Dissolve 400
where: g of sodium hydroxide (NaOH) in water and dilute to 1 L.
B 5 value of primary hydroxyl as determined in 38.2, and
44. Procedure
C 5 value of total hydroxyl as determined in 33.2.
44.1 Treatment Prior to Analysis—Remove uncombined
39. Precision and Bias sulfur as follows (Note 6): Dissolve 25 g of sample in
39.1 No statement on bias can be made as no reference approximately 300 mL of acetone, depending on the viscosity.
material is available as a standard. If the sample is of too high acetyl content to be directly soluble
SULFUR OR SULFATE CONTENT in acetone, cool in a dry ice cabinet overnight; then allow to
come to room temperature while tumbling or stirring. Filter the
40. Summary of Test Method solution, if necessary, through felt or a coarse sintered-glass
40.1 The sulfur or sulfate content of cellulose acetate is crucible. Precipitate with rapid stirring into a beaker or pail
measured by oxidizing the sample in a nitric acid-perchloric containing 2 to 3 L of acetic acid (1+49). Filter through a cloth
acid mixture and determining gravimetrically as barium sul- bag or a Büchner funnel and give two 15-min washes with
fate. To determine combined sulfur the sample must first be water using mechanical agitation. A little Na2CO3 may be
reprecipitated into dilute acid to remove noncombined sulfur added to the last wash to stabilize samples of high sulfur
compounds. content. Filter and dry overnight at 60°C.
40.2 The sulfur or sulfate content may also be determined NOTE 6—To analyze for total sulfur content omit this treatment.
by Test Method D 2929. In this case the X-ray method shall be
calibrated against the chemical method following in Sections 44.2 Decomposition:
42 to 45, and the sample shall be treated in accordance with 44.2.1 Weigh 10 6 0.1 g of cellulose acetate and transfer to
Section 44 if combined sulfur is to be determined. a clean, wide-mouth, 500-mL Erlenmeyer flask. Add 50 mL of
the HNO3-HClO4 mixture to the flask, and swirl the flask
41. Significance and Use gently to wet the sample thoroughly. Place the modified funnel
41.1 Sulfur and sulfate content indicates the amount of in the mouth of the flask and heat the flask carefully on a hot
sulfur in the cellulose ester either as inorganic salts (usually plate in a fume hood.
sulfates) or as organic sulfate (usually as sulfate ester com- NOTE 7—Precaution: Use the utmost care in handling the HNO3-
bined to the cellulose backbone). The presence of high levels of HClO4 mixture. If a spill occurs, wash down with plenty of water. Wear
sulfur and sulfate can be detrimental to the melt stability of the safety glasses or a face shield.
ester. 44.2.2 After the mixture becomes hot and less viscous,
42. Apparatus increase the heat of the hot plate. Continue the digestion until
42.1 Funnel, modified by cutting the stem off at the apex of all the sample has been oxidized and the thick reddish-brown
the funnel and fire polishing. fumes of nitrogen dioxide (NO2) have been expelled. At this
42.2 Crucibles, 30-mL, extra-fine porosity. point, white fumes will appear and a rather vigorous reaction
42.3 Oven, controlled at 120 to 125°C. will occur that is caused by the last traces of organic material
42.4 Muffle Furnace, controlled at 800 6 50°C. being oxidized and the HNO3 fuming off.
44.2.3 When this reaction starts, remove the flask from the
43. Reagents hot plate, swirl gently for a few seconds, and set it on the shelf
43.1 Acetone. in front of the hood until the reaction is complete. Place the
43.2 Acetic Acid (1+49)—Mix 1 volume of glacial acetic flask back on the hot plate and continue the digestion until the
acid with 49 volumes of water. HClO4 refluxes about half way up the side of the Erlenmeyer
43.3 Barium Chloride Solution (100 g/L)—Dissolve 100 g flask and about 5 mL is left in the flask. The HNO3-HClO4
of barium chloride (BaCl·2H2O) in water and dilute to 1 L. mixture should be clear and colorless. If it is not, set the flask
43.4 Hydrochloric Acid (1+1)—Mix 1 volume of concen- off the hot plate to cool and then add 3 to 5 mL of HNO3 (sp
trated hydrochloric acid (HCl, sp gr 1.19) with 1 volume of gr 1.42). Replace the flask on the hot plate and continue heating
water. until the HClO4 refluxes half way up the flask. Remove the
43.5 Nitric Acid (sp gr 1.42)—Concentrated nitric acid flask from the hot plate and allow the flask and its contents to
(HNO3). cool.
43.6 Nitric Acid (2+3)—Mix 2 volumes of concentrated 44.3 Determination of Barium Sulfate:
HNO3 (sp gr 1.42) with 3 volumes of water. 44.3.1 Wash the modified funnel top thoroughly with water,
43.7 Nitric Acid-Perchloric Acid Mixture—Mix 5 volumes collecting the rinsings in the flask. Add 50 ml of water. Swirl
of concentrated HNO3 with 1 volume of concentrated perchlo- the flask to mix the solution thoroughly. Add 2 drops of
ric acid (HClO4, 70 %). phenolphthalein indicator solution and neutralize the acid with
43.8 Phenolphthalein Indicator Solution (1 g/100 mL)— the NaOH solution to a faint pink. Acidify immediately with
Dissolve 1 g of phenolphthalein in 100 mL of ethyl alcohol HCl (1+1), dropwise, until the solution is just acid to phenol-
(95 %). phthalein; then add 2 mL of HCl (1+1).

7
 D 871
44.3.2 Filter through a 12.5-cm fine-porosity paper into a A 5 weight of sample, g,
clean 400-mL beaker. Wash the flask thoroughly with water, B 5 weight of crucible for sample, g,
filtering the washings through the paper. Finally wash the paper C 5 weight of crucible and BaSO4 for sample, g,
thoroughly with ten portions of hot water. Dilute the filtrate to C−B 5 weight of BaSO4 for sample,
approximately 200 mL. Place the beaker on the hot plate and D 5 weight of crucible for blank, g,
heat almost to boiling. Slowly add 10 mL of BaCl2 solution E 5 weight of crucible and BaSO4 for blank, g, and
from a pipet, stirring the solution during the addition. Do not E−D 5 weight of BaSO4 for blank, g.
add the BaCl2 solution rapidly, as from a graduate, since the
rapid addition will produce an impure precipitate. Remove the 46. Precision and Bias
stirring rod from the beaker and wash it with a stream of water 46.1 No statement on bias can be made as no reference
from the wash bottle, collecting the washings in the beaker. material is available as a standard.
Cover the beaker with a watch glass and keep the mixture near
the boiling temperature of 6 h or overnight. Do not allow the HEAT STABILITY
liquid to evaporate to dryness. 47. Summary of Test Method
44.3.3 Using suction, decant the supernatant liquid through
an extra-fine porosity porcelain filter crucible that has been 47.1 The heat stability of cellulose acetate is one indication
previously rinsed with acetone, ignited, and weighed to the of its quality. It is measured by heating the sample for a
nearest 0.1 mg. Transfer the precipitate with the aid of a stream specified time and temperature, observing it for amount and
of hot water. Always use a stirring rod in this transfer. Scrub the uniformity of color developed, and possibly also measuring the
sides and bottom of the beaker with a rubber policeman to loss of viscosity as a result of heating. Suggested times of
remove any adhering precipitate. The crucibles may be used to heating are 8 h at 180°C or 2 h at 190°C. The time and
collect several precipitates one on top of the other. Close temperature of heating, method of grading, and limits are
control of temperature and time of heating and cooling are matters for agreement between purchaser and the supplier.
necessary. Cleaning with hot water is generally sufficient; 48. Significance and Use
drastic attack with cleaning solution should be avoided.
44.3.4 Wash the precipitate on the filter until free of 48.1 The heat stability of a cellulose ester is one indication
chlorides by the following test: To 5 mL of wash water, of its quality.
collected in a separate test tube or on a watch glass, add 1 mL
49. Apparatus
of HNO3 (2+3) and 1 mL of AgNO3 solution. The appearance
of a milky white precipitate indicates the presence of chlorides, 49.1 Heater Block—A metal block of suitable size is heated
and the washing should therefore continue until the test is electrically and maintained at the specified temperature
negative. Do not attempt to get a completely negative test for within6 1°C. This is best accomplished by providing continu-
chloride. Discontinue washing when no more than a faint ous heat to hold the temperature a few degrees below the
opalescence is produced in the test. specified temperature, and providing intermittent additional
44.3.5 Finally pour a few millilitres of pure acetone through heat thermostatically controlled. Holes are drilled in the top of
the filter and suck it dry. Place the crucible in a larger crucible the block to hold test tubes, a thermoregulator, and a thermom-
or in a metal tray with perforated sides and bottom for eter. The block should be insulated.
protection and place it in an oven at 120 to 125°C for 1 h. Do 49.2 Test Tubes, either 18 by 150 mm or 20 by 150 mm,
not handle the crucibles with the fingers between ignition and fitted with corks. The corks shall be fitted with glass tubes the
the completion of weighing; use forceps. length of the cork and 4 mm in inside diameter or shall have a
44.3.6 Remove the crucible from the oven and ignite it for small V-shaped notch of equivalent cross-section cut in a
10 min in a muffle furnace at 800 6 50°C. Cool in a desiccator vertical position.
for 75 6 15 min and weigh to the nearest 0.0001 g. It is
50. Solvent
permissible to return the crucible to the oven for at least 15 min
before transferring to the desiccator. 50.1 Methylene Chloride-Methanol Mixture—Mix 9 parts
44.3.7 From time to time, and especially when using new by weight of methylene chloride with 1 part of methyl alcohol.
reagents, run a blank in duplicate in the reagents. If the weight
51. Heat Treatment
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 51.1 Place the sample, ground to pass a No. 20 (850-µm)
sample. 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 49.2.
45. Calculation Heat the tube and contents for 8 h at 180°C or as otherwise
45.1 Calculate the percentage of sulfur and sulfate as specified.
follows: 52. Dry Color Evaluation
Sulfur, % 5 ~@~C 2 B! 2 ~E 2 D!# 3 0.1374 3 100! / A (8) 52.1 Examine the heated sample for uniformity of color and
Sulfate, % 5 ~@~C 2 B! 2 ~E 2 D!# 3 0.4115 3 100 / A (9) for the presence of charred or decomposed spots. Compare the
color of the material at the bottom of the tube with standards
where: prepared as follows: Heat portions of a check batch of similar

8
 D 871
particle size, representative quality and stability, and accepted
by mutual agreement between the purchaser and the seller.
Pack portions of this check batch firmly in each of twelve
clean, dry test tubes and stopper with corks as described in
49.2. Heat the tubes at 180°C, or as otherwise specified,
remove one tube each 2 h, and mark the time of heating in
hours on each tube. This set of numbered tubes serves as the
color standards. They should be checked and renewed if
necessary every 6 months.
53. Solution Color Using Platinum - Cobalt Standards
53.1 Heat a 1-g sample for the specified time and tempera-
ture and, after cooling, examine for charred or decomposed
spots. Dissolve the heated sample in 15 mL of the methylene
chloride-methanol mixture. Compare the color of the solution
(viewing transversely) with test tubes of platinum-cobalt color
standards, prepared as described in Section 70. (It may be
necessary to prepare standards having as much as 2000 ppm of
platinum for this purpose or to dilute the sample solution
before grading.)
54. Solution Color by Spectrophotometer
FIG. 2 Wagner Capillary Tube Viscometer7
54.1 The color of the solution prepared as described in
Section 53 may also be measured spectrophotometrically.
Measure the absorbance at 400 nm against the solvent, using a 59.2 Water Bath—A constant-temperature water bath con-
suitable spectrophotometer with a 1-cm silica cell. trolled at 25.0 6 0.1°C and with a pump for circulating the
water through the viscometer jacket or tank.
55. Viscosity Change 59.3 Stop Clock or Watch, calibrated in tenths of a second.
55.1 Measure the intrinsic viscosity of the heated sample
and of an unheated sample as described in Sections 57 to 61 of 60. Procedure
this test method. The percentage loss of viscosity as the result 60.1 Sample Preparation—Dry about 0.26 g of sample in a
of heating is a measure of heat stability. weighing bottle at 105 6 3°C for 2 h, stopper, and cool in a
desiccator. Weigh the bottle containing the sample to the
56. Precision and Bias nearest 0.001 g, transfer the sample to a 250-mL flask, and
56.1 No statement on bias can be made as no reference reweigh the bottle. Pipet into the flask 100 mL of solvent at 25
material is available as a standard. 6 0.1°C. The solvent used should be mutually agreed upon by
the purchaser and the supplier. Suitable solvents are listed in
INTRINSIC VISCOSITY Table 1. After the sample is completely dissolved, place it in
the constant-temperature bath at 25°C along with a portion of
57. Summary of Test Method the solvent used, and allow sufficient time for both to come to
57.1 Intrinsic viscosity, expressed in decilitres of solution
per gram of solute, is determined by measuring the flow times TABLE 1 Solvents for Intrinsic Viscosity Determination
of a solution of known concentration and also of the solvent
Value of k for
used and making a calculation by means of the modified SolventA Ingredients, weight % Calculation
Baker-Philippoff equation. (see 61.2)
A 90 % acetoneB 10
NOTE 8—By expressing concentration in grams per millilitre rather
10 % ethyl alcoholC
than grams per decilitre, the result will be limiting viscosity number B acetoneB 10
instead of intrinsic viscosity, and will be 100 times greater. C or D 90 % methylene chlorideD 3
10 % ethyl alcoholC
58. Significance and Use E 96 % acetoneB 10
4 % water
58.1 Intrinisic viscosity number can be used to estimate the F 90 % methylene chlorideD 3
molecular weight of a cellulose ester by using the Mark- 10 % methanolE
Houwink equation and constants measured for the solvent, A
Solvent designations conform to those used in Table 2 for viscosity determi-
temperature, and ester of concern. nations.
B
Acetone (99.4 6 0.1 %) containing 0.3 to 0.5 % water and under 0.3 % ethyl
alcohol.
59. Apparatus C
Ethyl alcohol (95 volume %). Formula 2B or 3A denatured ethyl alcohol may be
59.1 Capillary Viscometer, such as the Wagner apparatus used.
D
Methylene chloride having a boiling range of 39.2 to 40.0 C and less than
(Fig. 2) or an Ostwald-Fenske-Cannon pipet, that will give a 0.001 % acidity calculated as HCl.
flow time for the solvent of not less than 70 s. E
Methyl alcohol (sp gr 20/20°C 5 0.785 to 0.795).

9
 D 871
temperature before making the viscosity measurements. Dur- TABLE 2 Solutions for Viscosity Determination
ing this conditioning period, water at 25°C should be circulat- Formula
ing through the water jacket of the viscometer to allow ample A B C D E F
time for the pipet to reach temperature equilibrium. Ingredients, weight %
60.2 Viscosity Measurements—Rinse the reservoir and the Cellulose acetate 20A 20A 20B 15C 20A 10C
outside of the capillary tube thoroughly with solvent. Rinse the AcetoneD 72 80 ... ... ... ...
inside of the capillary tube twice by alternately applying Acetone, 96 % ... ... ... ... ... ...
Water, 4 %
pressure at points B and A (Fig. 2). Discard the wash portion of Ethyl alcoholE 8 ... 8 8.5 ... ...
the solvent. Pour more solvent into the reservoir and allow Methyl alcoholF ... ... ... ... ... 9
several minutes for complete drainage and thermal equilibrium Methylene chlorideG ... ... 72 76.5 ... 81
to be obtained. Adjust the outer meniscus to a reference point, Typical Solution Densities, g/mL at 25 C
D, that will give a flow time between 70 and 100 s. Apply air 0.84 0.86 1.25 1.23 0.86 1.24
pressure at B to force the solvent up through the capillary past A
Acetyl content 40.5 %, max.
the upper timing mark, C, on the measuring bulb, E. Record the B
Acetyl content 40.5 to 42.7 %.
C
time in seconds required for the meniscus to fall between the Acetyl content 42.7 to 44.8 %.
D
Acetone (99.4 6 0.1 %) containing 0.3 to 0.5 % water and under 0.3 % ethyl
timing marks, C and F. Take a minimum of two readings. alcohol.
Repeat these operations, substituting the solution for the E
Ethyl alcohol (95 volume %). Formula 2B or 3A denatured ethyl alcohol may be
solvent. used.
F
Methyl alcohol (sp gr 20/20 C 5 0.785 to 0.795).
G
Methylene chloride having a boiling range of 39.2 to 40.0°C and less than
61. Calculation 0.001 % acidity calculated as HCl.
61.1 Calculate the relative viscosity, hrel, as follows:
hrel 5 t1/t2 (10) material is available as a standard.
where: COLOR AND HAZE
t1 5 flow time of solution, and
t2 5 flow time of solvent. 67. Summary of Test Method
61.2 Calculate the intrinsic viscosity, [h], as follows: 67.1 Color and haze determinations on cellulose ester solu-
@h# 5 ~k/c! @antilog~log hrel/k! 2 1# (11) tions are made by comparison with standards. Simultaneous
measurement of these properties is desirable because haze
where: reduces the amount of color observed.
k 5 values from Table 1, and
c 5 concentration in grams per decilitre (Note 8 in Section 68. Significance and Use
57). 68.1 Solution color and haze of a cellulose ester is a
62. Precision and Bias measurement of the optical properties of cellulose esters when
dissolved in a specific solvent.
62.1 No statement on bias can be made as no reference
material is available as a standard. 69. Apparatus
VISCOSITY 69.1 Light Box—A suitable light box (Fig. 3 and Fig. 4) is
described as follows. The light source consists of a mercury
63. Significance and Use vapor bulb, which requires an auto transformer for the current
63.1 A measurement of viscosity is of great practical utility source. The bulb is mounted horizontally across the lower front
in determining the proper processing equipment and process
concentrations for cellulose esters.
64. Procedure
64.1 Solution—Dry the sample for 1 to 2 h at 105 6 3°C
and cool in a desiccator. Prepare a solution of the dried sample
in a solvent and at a concentration mutually agreed upon by the
purchaser and the seller. Suitable solutions are listed in Table 2.
64.2 Viscosity Determination—Prepare the solution and
measure the viscosity in accordance with Test Method D 1343,
(Note 10 in Section 71 of these methods).
65. Report
65.1 Report the results in poises, unless otherwise specified.
The viscosity values shall be prefixed with the letter A, B, C,
etc., corresponding to the formula of the solution employed.
66. Precision and Bias
66.1 No statement on bias can be made as no reference FIG. 3 Color and Haze Apparatus

10
 D 871

Metric Equivalents
in. mm in. mm in. mm in. mm in. mm
⁄
18 3.2 1⁄
34 44.4 3⁄
34 95.2 6⁄
14 158.8 8⁄
12 215.9
⁄
12 12.7 21⁄2 63.5 43⁄4 120.6 71⁄2 190.5 13 330.2
13 16⁄ 20.6 3 76.2 5 127.0 81⁄4 209.6 171⁄2 444.5
1 25.4 31⁄4 82.6 6 152.4 83⁄8 212.7 201⁄2 520.7

FIG. 4 Color and Haze Apparatus (Details)

part of a plywood box 350-mm wide, 430-mm high, and 70. Reference Standards
330-mm deep. This box is lined with a heat resistant board and 70.1 Color Standards—A color standard containing 500
is painted black inside, except that the inside back surface ppm of platinum may be purchased or the solution may also be
toward the viewer is white. A bottle holder large enough to hold prepared as follows: Dissolve 1.245 g of potassium platinum
four bottles is built onto the front of the light box, and a 63.5 chloride (K2PtCl6), containing 0.500 g of platinum, and 1.000
by 152.4-mm horizontal viewing hole is cut through the front g of crystallized cobalt chloride (CoCl2·6H2O), containing
of the box. This opening is covered with clear glass, and a 0.248 g of cobalt, in water, add 100 mL of HCl (sp gr 1.19), and
6.4-mm strip of black tape is fastened to the glass horizontally dilute to 1 L with water. Prepare standards containing 50, 60,
to aid in judging haze in the solution. Holes are cut in the 70, 80, 90, 100, 125, 150, 175, 200, 250, 300, 350, 400 and 500
bottom and top of the box for cooling by air convection. For ppm of platinum by diluting suitable aliquots of the standard
continuous use, forced circulation of air would be desirable. A solution to 500 mL with water. Place these standards in the
black metal baffle over the bulb prevents direct light on the special bottles (see 69.2), taking care to select bottles with
viewing glass. good clarity and free of flaws. Label and cap tightly.
69.2 Sample Bottles—The bottles used for the sample solu- 70.2 Haze Standards—Prepare haze standards by diluting a
tions are French square bottles, 16-oz, with screw caps. These stock solution having a turbidity of 1000 ppm. Prepare bottles
same bottles may be used for the color and haze standards. containing 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 125, 150,
NOTE 9—These bottles may also be used for determination of viscosity, 175, 200, and 400 ppm of turbidity, label, and cap tightly.
as described in 64.2. NOTE 10—The previously recommended stock solution for preparing
69.3 Cap Liners—Cap liners shall be of a composition not these standards was made from fuller’s earth, water, and hydrochloric
acid. This solution is no longer available. A comparable stock solution can
affected by the solvents used. Liners of fiber board covered be made using a diatomaceous earth. To obtain haze levels equivalent to
with cellophane or aluminum foil are usually satisfactory, but the fuller’s earth standard, 1.1 parts diatomaceous should be used in place
vinyl resin or waxed liners may cause interference with of 1.0 parts of fuller’s earth in preparing the aqueous suspension. No
viscosity, color, or haze measurements. hydrochloric acid is needed.

11
 D 871
71. Procedure NOTE 11—When viscosity, color, and haze determinations, and an
observation of general appearance are to be made on a cellulose ester
71.1 Prepare the solution to be graded by dissolving the sample, a considerable saving in time can be made by using one solution
cellulose ester in the specified amount and kind of solvent, in in a square bottle for all three determinations. Dry the cellulose ester as
one of the square bottles. See Table 2 for suitable solutions. At required for the viscosity determination, prepare the solution carefully,
least 350 mL are required. Tumble until a uniform solution is and allow the bottle to stand long enough to form a thick solution before
obtained. Allow the solution to stand until it is free of bubbles tumbling, to avoid solvent loss around the cap. Use a large enough sample
before grading it for color and haze: to provide at least 350 mL of solution in the bottle. Measure the viscosity
as described in Test Method D 1343, and then rate the color and haze.
71.2 Place the bottle containing the solution to be graded at
the front of the shelf on the apparatus and place a similar bottle 72. Precision and Bias
containing water behind it. Place the freshly shaken haze
standard at the front of the shelf beside the bottle containing the 72.1 No statement on bias can be made as no reference
solution to be tested and place the color standard behind it. material is available as a standard.
Determine the amount of color and haze in the solution by
changing the color and haze standards until as good a match as 73. Keywords
possible has been obtained. The haze standards settle out 73.1 apparent acetyl; ash; cellulose acetate; cellulose ester;
quickly so they must be reshaken at short intervals. Report color; free acidity; haze; hydroxyl; intrinsic viscosity; sulfate
results in parts per million for both color and haze. content

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with any item mentioned in this standard. Users of this standard are expressly advised that determination of the validity of any such
patent rights, and the risk of infringement of such rights, are entirely their own responsibility.

This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years and
if not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standards
and should be addressed to ASTM Headquarters. Your comments will receive careful consideration at a meeting of the responsible
technical committee, which you may attend. If you feel that your comments have not received a fair hearing you should make your
views known to the ASTM Committee on Standards, 100 Barr Harbor Drive, West Conshohocken, PA 19428.

12