ASTM D817-96(2010)
(Test Method)Standard Test Methods of Testing Cellulose Acetate Propionate and Cellulose Acetate Butyrate
Standard Test Methods of Testing Cellulose Acetate Propionate and Cellulose Acetate Butyrate
SIGNIFICANCE AND USE
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 and optical clarity of a cellulose ester in melt processing or act as a potential source of insolubles when the ester is used in solution.
SCOPE
1.1 These test methods cover procedures for the testing of cellulose acetate propionates and acetate butyrates. These esters may vary widely in composition and properties, so certain of the procedures can be used only in the ranges of composition where they are suitable.
1.2 The values stated in SI units are to be regarded as the standard. The values given in parentheses are for information only.
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NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: D817 − 96 (Reapproved 2010)
StandardTest Methods of Testing
Cellulose Acetate Propionate and Cellulose Acetate
Butyrate
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.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope D2929Test Method for Sulfur Content of Cellulosic Mate-
rials by X-Ray Fluorescence
1.1 These test methods cover procedures for the testing of
D5897Test Method for Determination of Percent Hydroxyl
cellulose acetate propionates and acetate butyrates. These
on Cellulose Esters by Potentiometric Titration—
esters may vary widely in composition and properties, so
Alternative Method
certain of the procedures can be used only in the ranges of
2.2 ASTM Adjuncts:
composition where they are suitable.
Color and Haze Apparatus
1.2 The values stated in SI units are to be regarded as the
3. Reagents
standard. The values given in parentheses are for information
only.
3.1 Purity of Reagents—Reagent grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that
1.3 The test procedures appear in the following sections:
all reagents shall conform to the specifications of the Commit-
Sections
tee onAnalytical Reagents of theAmerican Chemical Society,
Acetyl Propionyl or Butyryl Contents 28-37
Acetyl Content, Apparent 18-27
where such specifications are available. Other grades may be
Acidity, Free 12-17
used, provided it is first ascertained that the reagent is of
Ash 7-10
sufficiently high purity to permit its use without lessening the
Color and Haze 77-81
Heat Stability 57-65
accuracy of the determination.
Hydroxyl Content 38-44
Hydroxyl Content, Primary 46-50
4. Conditioning
Intrinsic Viscosity 67-71
Moisture Content 5-6 4.1 Conditioning—Condition the test specimens at 23 6
Sulfur or Sulfate Content 51-56
2°C(73.4 63.6°F)and50 65%relativehumidityfornotless
Viscosity 74-75
than 40 h prior to test in accordance with Procedure A of
Limiting Viscosity Number 67-71
Practice D618, for those tests where conditioning is required.
1.4 This standard does not purport to address the safety
In cases of disagreement, the tolerances shall be 61°C
concerns, if any, associated with its use. It is the responsibility
(61.8°F) and 62% relative humidity.
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 65%
limitations prior to use.
relative humidity, unless otherwise specified in the test meth-
2. Referenced Documents
ods. In cases of disagreements, the tolerances shall be 61°C
(61.8°F) and 62% relative humidity.
2.1 ASTM Standards:
D618Practice for Conditioning Plastics for Testing
MOISTURE CONTENT
D1343Test Method for Viscosity of Cellulose Derivatives
by Ball-Drop Method 5. Procedure
5.1 Transfer about5gofthe sample to a tared, low,
wide-form weighing bottle and weigh to the nearest 0.001 g.
These test methods are under the jurisdiction of ASTM Committee D01 on
Paint and Related Coatings, Materials, and Applications and are the direct
responsibility of Subcommittee D01.36 on Cellulose and Cellulose Derivatives. Available from ASTM International Headquarters. Order Adjunct No.
CurrenteditionapprovedJune1,2010.PublishedJuly2010.Originallyapproved ADJD0817. Original adjunct produced in 1969.
ϵ1
in 1944. Last previous edition approved in 2004 as D817–96(2004) . DOI: Reagent Chemicals, American Chemical Society Specifications, American
10.1520/D0817-96R10. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
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 service@astm.org. 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.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D817 − 96 (Reapproved 2010)
Dry in an oven for2hat105 6 3°C. Remove the bottle from 12.2 Methyl Red Indicator Solution (0.4 g/L)—Dissolve 0.1
the oven, cover, cool in a desiccator, and weigh. g of methyl red in 3.72 mL of 0.1000 N NaOH solution and
dilute to 250 mL with water. Filter if necessary.
6. Calculation
12.3 Phenolphthalein Indicator Solution (1 g/100 mL)—
6.1 Calculate the percentage of moisture as follows:
Dissolve 1gphenolphthalein in 100 mL of ethyl alco-
hol (95%).
Moisture, % 5 A/B 3100 (1)
~ !
12.4 Sodium Hydroxide, Standard Solution (0.01 N)—
where:
Prepareandstandardizea0.01 Nsolutionofsodiumhydroxide
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 Shake5gofthesample,correctedformoisturecontent
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.
13.2 Runablankdeterminationonthewater,usingthesame
8. Procedure
volume as was used in extracting the sample.
8.1 Drythesamplefor2hat105 63°Candweigh10to50
14. Calculation
g,tothenearest0.01to0.1g,dependingonitsashcontentand
14.1 Calculate the percentage of acidity as free acetic acid
the accuracy desired. Burn directly over a flame in a 100-mL
as follows:
taredplatinumcruciblethathasbeenheatedtoconstantweight
and weighed to the nearest 0.1 mg.Add the sample in portions
Freeaceticacid, % 5 A 2 B C 30.06 /W 3100 (3)
$@~ ! # %
if more than 10 g is taken. The sample should burn gently and
where:
the portions should be added as the flame subsides. Continue
A = NaOH solution used to titrate the sample, mL,
heating with a burner only as long as the residue burns with a
B = NaOH solution used to titrate the blank, mL,
flame.Transfer the crucible to a muffle furnace and heat at 550
C = normality of the NaOH solution, and
to 600°C for 3 h, or longer if required, to burn all the carbon.
W = sample used, g.
Allowthecrucibletocoolandthentransferit,whilestillwarm,
to a desiccator. When the crucible has cooled to room tem-
Test Method B—For Samples Containing More than About
perature, weigh accurately to the nearest 0.1 mg.
7 % Propionyl or Butyryl and Particularly Suitable for
Samples Containing More than 30 % Propionyl or Butyryl
9. Calculation
15. Procedure
9.1 Calculate the percentage of ash as follows:
15.1 Dissolve 10.0 g of the sample, corrected for moisture
Ash, % 5 A/B 3100 (2)
~ !
content if necessary, in 200 mL of neutral acetone plus 20 mL
where:
of water. When completely dissolved, add 50 mLof water and
shakewelltoprecipitatetheesterinafinelydividedform.Add
A = ash, g, and
B = sample used, g.
3 drops of methyl red indicator solution and titrate to a
lemon-yellow end point and 0.01 N NaOH solution.
10. Precision and Bias
15.2 Make a blank determination on the reagents.
10.1 No statement on bias can be made as no reference
16. Calculation
material is available as a standard.
16.1 Calculate the free acid content as acetic acid as
FREE ACIDITY
directed in Section 14.
17. Precision and Bias
11. Significance and Use
17.1 No statement on bias can be made as no reference
11.1 Freeacidityisameasureofunesterifiedorganicacidin
material is available as a standard.
the ester.The presence of high levels of free acid is potentially
detrimental to melt processing of the ester and can impact the
APPARENT ACETYL CONTENT
odor of the ester.
18. Scope
12. Reagents
18.1 The test methods described in the following Sections
12.1 Acetone, neutral. 20 to 26 cover the determination of the saponification value of
D817 − 96 (Reapproved 2010)
thesamplecalculatedaspercentageofapparentacetyl,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 (H SO ).
2 4
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
Dissolve1gof 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
MethodAis recommended for samples having less than about
22. Procedure
35% propionyl or butyryl and Test Method B for samples
22.1 Dry the ground well-mixed sample in weighing bottle
having more than that amount.
for2hat105 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
Erlenmeyerflask.Prepareablankbydryingapproximately3.8
19.1 Apparent acetyl content is a measure of the saponifi-
gofpotassiumacidphthalateandweighingitbydifferenceinto
cation value of the ester. Apparent acetyl value is required in
a flask as described above. Carry the blank through the entire
the calculation of acetyl, propionyl, and butyryl content in
procedure.
36.1.
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
blank and the sample or by refilling the 15-mLburet. If desired, however,
20.1 Weighing Bottle, glass-stoppered, 15-mL capacity,
the potassium acid phthalate may be omitted.
25-mm diameter by 50 mm high.
22.2 For acetone-soluble sample, put the sample into solu-
20.2 Tray, copper or aluminum, approximately 137 mm
tion as follows: Add 150 mL of acetone and 5 to 10 mL of
square, containing 25 compartments 25 mm square. Each
water and swirl to mix. Stopper the flask and allow it to stand
compartment shall have the correct dimensions to contain one
with occasional swirling until solution is complete. Solution
weighingbottle.Theentiretrayshallfitinsideadesiccatorand
may be hastened by magnetic stirring or by any suitable
should have a basket-type handle to facilitate the introduction
mechanical shaking that will provide a gentle rocking type of
and removal of the tray (convenient but not essential).
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,
22.3 For acetone-insoluble samples of low propionyl or
automatic zero, 30-mL for NaOH solution (40 g/L).
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
22.3.1 Gently rotate the flask by hand to distribute and
H SO .
2 4
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.
Stopper the flask and allow it to stand undisturbed for 10 min.
20.6 Magnetic Stirrer, for single flask.
Carefully add 30 mLof 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
solution is complete. Magnetic stirring or gentle mechanical
21. Reagents
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
solutiontoamixtureof150mLacetoneand100mLhotwater,
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 H SO .Add another 30-mLportion of 1.0 N NaOH
2 4
is not available, spread the sample in a thin layer over the
solutionto100mLofhotwater,allowtostandfor30min,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
10 min. Heat the solution just to boiling and swirl or stir for 5
21.3 Pyridine.
min. Again heat to boiling and swirl or stir for 10 min.
21.4 Sodium Hydroxide Solution(40g/L)—Dissolve40gof
Continuetoheatandstiruntilthemixtureishomogeneousand
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,
D817 − 96 (Reapproved 2010)
NOTE 4—When equal volumes of alkali or acid are added to samples
no further heating is necessary. Cool the flask, add 30 mL of
andblank,theseamountscancelout.Thusonlytheamountsofeachadded
acetone, and swirl or stir for 5 min.
in the titration enter into the calculations. Use of potassium acid phthalate
22.4 Add 30 mL of NaOH solution (40 g/L) with constant in the blank is recommended.When it is not used,
...
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