ASTM D817-12(2019)
(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
7.1 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 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.
1.3 The test procedures appear in the following sections:
Sections
Acetyl Propionyl or Butyryl Contents
28 – 37
Acetyl Content, Apparent
18 – 27
Acidity, Free
12 – 17
Ash
7 – 10
Color and Haze
77 – 81
Heat Stability
57 – 65
Hydroxyl Content
38 – 44
Hydroxyl Content, Primary
46 – 50
Intrinsic Viscosity
67 – 71
Moisture Content
5-6
Sulfur or Sulfate Content
51 – 56
Viscosity
74-75
Limiting Viscosity Number
67 – 71
1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety, health, and environmental practices and determine the applicability of regulatory limitations prior to use.
1.5 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.
General Information
Relations
Standards Content (Sample)
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 (Reapproved 2019)
Standard Test 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 2. Referenced Documents
1.1 These test methods cover procedures for the testing of 2.1 ASTM Standards:
cellulose acetate propionates and acetate butyrates. These D618Practice for Conditioning Plastics for Testing
esters may vary widely in composition and properties, so D1343Test Method for Viscosity of Cellulose Derivatives
certain of the procedures can be used only in the ranges of by Ball-Drop Method
composition where they are suitable. D2929Test Method for Sulfur Content of Cellulosic Mate-
rials by X-Ray Fluorescence
1.2 The values stated in SI units are to be regarded as the
D5897Test Method for Determination of Percent Hydroxyl
standard. The values given in parentheses are for information
on Cellulose Esters by Potentiometric Titration—
only.
Alternative Method
1.3 The test procedures appear in the following sections:
3. Reagents
Sections
Acetyl Propionyl or Butyryl Contents 28–37
3.1 Purity of Reagents—Reagent grade chemicals shall be
Acetyl Content, Apparent 18–27
Acidity, Free 12–17 used in all tests. Unless otherwise indicated, it is intended that
Ash 7–10
all reagents shall conform to the specifications of the Commit-
Color and Haze 77–81
tee onAnalytical Reagents of theAmerican Chemical Society,
Heat Stability 57–65
where such specifications are available. Other grades may be
Hydroxyl Content 38–44
Hydroxyl Content, Primary 46–50
used, provided it is first ascertained that the reagent is of
Intrinsic Viscosity 67–71
sufficiently high purity to permit its use without lessening the
Moisture Content 5-6
accuracy of the determination.
Sulfur or Sulfate Content 51–56
Viscosity 74-75
Limiting Viscosity Number 67–71
4. Conditioning
1.4 This standard does not purport to address all of the
4.1 Conditioning—Condition the test specimens at 23 6
safety concerns, if any, associated with its use. It is the
2°C(73.4 63.6°F)and50 65%relativehumidityfornotless
responsibility of the user of this standard to establish appro-
than 40 h prior to test in accordance with Procedure A of
priate safety, health, and environmental practices and deter-
Practice D618, for those tests where conditioning is required.
mine the applicability of regulatory limitations prior to use.
In cases of disagreement, the tolerances shall be 61°C
1.5 This international standard was developed in accor-
(61.8°F) and 62% relative humidity.
dance with internationally recognized principles on standard-
4.2 Test Conditions—Conduct tests in the Standard Labora-
ization established in the Decision on Principles for the
tory Atmosphere of 23 6 2°C (73.4 6 3.6°F) and 50 65%
Development of International Standards, Guides and Recom-
mendations issued by the World Trade Organization Technical
Barriers to Trade (TBT) Committee.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website.
1 3
These test methods are under the jurisdiction of ASTM Committee D01 on ACS Reagent Chemicals, Specifications and Procedures for Reagents and
Paint and Related Coatings, Materials, and Applications and are the direct Standard-Grade Reference Materials, American Chemical Society, Washington,
responsibility of Subcommittee D01.36 on Cellulose and Cellulose Derivatives. DC. For suggestions on the testing of reagents not listed by theAmerican Chemical
Current edition approved Dec. 1, 2019. Published December 2019. Originally Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset,
approved in 1944. Last previous edition approved in 2012 as D817–12. DOI: U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharma-
10.1520/D0817-12R19. copeial Convention, Inc. (USPC), Rockville, MD.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D817 − 12 (2019)
relative humidity, unless otherwise specified in the test meth- FREE ACIDITY
ods. In cases of disagreements, the tolerances shall be 61°C
(61.8°F) and 62% relative humidity.
11. Significance and Use
11.1 Freeacidityisameasureofunesterifiedorganicacidin
MOISTURE CONTENT
the ester.The presence of high levels of free acid is potentially
detrimental to melt processing of the ester and can impact the
5. Procedure
odor of the ester.
5.1 Transfer about5gofthe sample to a tared, low,
wide-form weighing bottle and weigh to the nearest 0.001 g.
12. Reagents
Dry in an oven for2hat105 6 3°C. Remove the bottle from
12.1 Acetone, neutral.
the oven, cover, cool in a desiccator, and weigh.
12.2 Methyl Red Indicator Solution (0.4 g/L)—Dissolve 0.1
g of methyl red in 3.72 mL of 0.1000 N NaOH solution and
6. Calculation
dilute to 250 mL with water. Filter if necessary.
6.1 Calculate the percentage of moisture as follows:
12.3 Phenolphthalein Indicator Solution (1 g/100 mL)—
Moisture, % 5 A/B 3100 (1)
~ !
Dissolve 1gphenolphthalein in 100 mL of ethyl alco-
hol (95%).
where:
12.4 Sodium Hydroxide, Standard Solution (0.01 N)—
A = weight loss on heating, g, and
Prepareandstandardizea0.01 Nsolutionofsodiumhydroxide
B = sample used, g.
(NaOH).
ASH
Test Method A—For Samples Containing Not More than
About 30 % Propionyl or Butyryl
7. Significance and Use
7.1 Ash content gives an estimate of the inorganic content
13. Procedure
of cellulose ester samples. The presence of high levels of
13.1 Shake5gofthesample,correctedformoisturecontent
inorganic content (ash) can be detrimental to the melt stability
if necessary, in a 250-mL Erlenmeyer flask with 150 mL of
and optical clarity of a cellulose ester in melt processing or act
freshly boiled, cold water. Stopper the flask and allow it to
as a potential source of insolubles when the ester is used in
stand for 3 h. Filter off the cellulose ester and wash it with
solution.
water. Titrate the combined filtrate and washings with 0.01 N
NaOH solution, using phenolphthalein indicator solution.
8. Procedure
13.2 Runablankdeterminationonthewater,usingthesame
8.1 Drythesamplefor2hat105 63°Candweigh10to50
volume as was used in extracting the sample.
g,tothenearest0.01to0.1g,dependingonitsashcontentand
the accuracy desired. Burn directly over a flame in a 100-mL
14. Calculation
taredplatinumcruciblethathasbeenheatedtoconstantweight
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
the portions should be added as the flame subsides. Continue
Freeaceticacid, % 5 A 2 B C 30.06 /W 3100 (3)
$@~ ! # %
heating with a burner only as long as the residue burns with a
where:
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,
Allowthecrucibletocoolandthentransferit,whilestillwarm,
C = normality of the NaOH solution, and
to a desiccator. When the crucible has cooled to room
W = sample used, g.
temperature, weigh accurately to the nearest 0.1 mg.
Test Method B—For Samples Containing More than About
9. Calculation
7 %Propionyl or Butyryl and Particularly Suitable for
Samples Containing More than 30 % Propionyl or Butyryl
9.1 Calculate the percentage of ash as follows:
Ash, % 5 A/B 3100 (2)
~ !
15. Procedure
where:
15.1 Dissolve 10.0 g of the sample, corrected for moisture
A = ash, g, and
content if necessary, in 200 mL of neutral acetone plus 20 mL
B = sample used, g.
of water. When completely dissolved, add 50 mLof water and
shakewelltoprecipitatetheesterinafinelydividedform.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.
D817 − 12 (2019)
16. Calculation 20.7 Magnetic Stirrer, capacity twelve or more flasks.
16.1 Calculate the free acid content as acetic acid as 20.8 Stirring Bars, stainless steel Type 416, length 50 mm,
directed in Section 14. diameter 5 to 6 mm or equivalent, dimensions not critical.
17. Precision and Bias
21. Reagents
17.1 No statement on bias can be made as no reference 21.1 Acetone—Add one 30-mL portion of 1.0 N NaOH
material is available as a standard. solutiontoamixtureof150mLacetoneand100mLhotwater,
allow to stand with frequent swirling for 30 min, and titrate
APPARENT ACETYL CONTENT
with 1.0 N H SO .Add another 30-mLportion of 1.0 N NaOH
2 4
solutionto100mLofhotwater,allowtostandfor30min,and
18. Scope
titrate as above.The difference between the two titrations shall
18.1 The test methods described in the following Sections
not exceed 0.05 mL.
20 to 26 cover the determination of the saponification value of
21.2 Dimethyl Sulfoxide.
thesamplecalculatedaspercentageofapparentacetyl,equiva-
21.3 Pyridine.
lent weight 43. This value is required in the calculation of
acetyl and propionyl or butyryl contents in 36.1.
21.4 Sodium Hydroxide Solution (40 g/L)—Dissolve40gof
sodium hydroxide (NaOH) in water and dilute to 1 L.
18.2 The test method used should be specified or agreed
upon. The choice depends on the propionyl or butyryl content
21.5 Sodium Hydroxide, Standard Solution (0.1 N)—
and the physical condition of the sample. Ordinarily, Test
Prepare and standardize a 0.1 N solution of NaOH.
MethodAis recommended for samples having less than about
21.6 Sulfuric Acid Standard (1.0 N)—Prepare and standard-
35% propionyl or butyryl and Test Method B for samples
ize a 1.0 N solution of sulfuric acid (H SO ).
2 4
having more than that amount.
21.7 Phenolphthalein Indicator Solution (1 g/100 mL)—
18.3 This international standard was developed in accor-
Dissolve1gof phenolphthalein in 100 mL of ethyl alcohol
dance with internationally recognized principles on standard-
(95%).
ization established in the Decision on Principles for the
Development of International Standards, Guides and Recom-
22. Procedure
mendations issued by the World Trade Organization Technical
22.1 Dry the ground well-mixed sample in weighing bottle
Barriers to Trade (TBT) Committee.
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
avoiding errors caused by using a different buret for the titration of the
20. Apparatus
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
essential that complete solution be effected.
20.3 Buret, automatic zero, 35-mL, 25-mL bulb, stem
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
two methods:
20.4 Buret, automatic zero, 15-mL, 10-mL bulb, stem
22.3.1 Gently rotate the flask by hand to distribute and
graduated from 10 to 15 mL in 0.05-mL increments, for 1 N
spread the sample in a thin layer over the bottom of the flask.
H SO .
2 4
Add 70 mL of acetone to the flask and swirl gently until the
20.5 Buret, 5-mL, in 0.01 or 0.1-mL divisions, for back
sample particles are completely wetted and evenly dispersed.
titration with 0.1 N NaOH solution.
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
D817 − 12 (2019)
the flask, pouring the solvent down the sides of the flask to Acetyl, % 5 D 2 C N 2 B 2 A N 1P 30.04305 /W 3100
$@~ ! ~ ! # %
a b
wash down any sample particles clinging to the side. Stopper
(4)
the flask and allow it to stand with occasional swirling until
P 5 ~GH 31000!/204.2
solution is complete. Magnetic stirring or gentle mechanical
agitation that will not splash the solution is recommended.
where:
When solution appears to be complete, add 50 mL of acetone
A = NaOHsolutionrequiredfortitrationofthesample,mL,
and swirl or stir for 5 min. Proceed in accordance with 22.4.
B = NaOH solution required for titration of the blank, mL,
22.3.2 Dimethyl sulfoxide is the preferred solvent, but if it
N = normality of the NaOH solution,
b
is not available, spread the sample in a thin layer over the
C =H SO required for titration of the sample, mL
2 4
bottom
...
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