ASTM C323-56(2006)

Standard Test Methods for Chemical Analysis of Ceramic Whiteware Clays

ABSTRACT
These test methods cover the chemical analysis of clays used in the manufacture of ceramic whitewares. Determine moisture on the sample in its ordinary air-dried condition. Determine all other percentage compositions on moisture-free samples and report accordingly on a moisture-free basis. Make blank determinations on the reagents for each constituent in the whiteware clay and deduct this blank in each case. The sample shall be heated to a constant weight at a given temperature; the loss in weight is recorded as moisture. For the determination of the silica blank, approximately 0.25 g of alumina should be added as aluminium chloride. The procedure for the determination of iron, aluminium, and titanium oxide blank are presented in details. The procedure for the determination of iron oxide, titania, alumina, lime, magnesia, and alkalies blank are discussed and presented in details.
SCOPE
1.1 These test methods cover the chemical analysis of clays used in the manufacture of ceramic whitewares.
1.2 The analytical procedures appear in the following order:Note 1
These test methods have been compiled as standard procedures for use in referee analyses. These test methods, however, when the determination of iron oxide as Fe2O3 is involved, are not intended to preclude the use of other procedures that give results within the permissible variations. For the sake of uniformity the classical Zimmerman-Reinhardt procedure is specified for the determination of iron oxide. It is recognized that numerous other procedures are equally accurate and often more convenient. The other procedures commonly in use include reduction of an oxidized solution with zinc or other metal, and titration with standard potassium permanganate (KMnO4) or potassium dichromate (K2Cr2O 7) solution, as well as titration with a standard solution of titanous chloride in an oxidized solution. These procedures shall be considered acceptable, provided the analyst has obtained results by his special procedure that check with the Zimmerman-Reinhardt procedure within the limits specified in Section . It is suggested that National Institute of Standards and Technology standard samples be used for checking the accuracy of procedures.
It will be understood that the making of a complete analysis of a ceramic whiteware clay is a difficult procedure requiring a wide knowledge of the chemistry involved in the operations and a thorough training in carrying out the work. A skilled analyst of good training is therefore required to do the work. The descriptions here given cover the vital points of procedure, but frequent reference in regard to the details of the various manipulations should be made to "Applied Inorganic Analysis" by Hillebrand and Lundell and to similar publications. Particularly in the determination of alumina, reference should be made to  Scientific Paper No. 286  of the National Bureau of Standards.
1.3 The values stated in acceptable metric units are to be regarded as the standard. The values given in parentheses are for information only.
This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

General Information

• Status: Historical
• Publication Date: 14-Feb-2006
• ICS: 91.100.25 - Terracotta building products
• Technical Committee: C21 - Ceramic Whitewares and Related Products
• Drafting Committee: C21.04 - Raw Materials

Relations

• Replaces: ASTM C323-56(1999) - Standard Test Methods for Chemical Analysis of Ceramic Whiteware Clays
• Effective Date: 15-Feb-2006
• Replaced By: ASTM C323-56(2011) - Standard Test Methods for Chemical Analysis of Ceramic Whiteware Clays
• Effective Date: 01-Mar-2011

Standards Content (Sample)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation:C323–56 (Reapproved 2006)
Standard Test Methods for
Chemical Analysis of Ceramic Whiteware Clays
This standard is issued under the fixed designation C323; 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.
determination of alumina, reference should be made to Scientific Paper
1. Scope
No. 286 of the National Bureau of Standards.
1.1 These test methods cover the chemical analysis of clays
1.3 The values stated in acceptable metric units are to be
used in the manufacture of ceramic whitewares.
regarded as the standard. The values given in parentheses are
1.2 The analytical procedures appear in the following order:
for information only.
Section
Moisture 7 1.4 This standard does not purport to address all of the
Loss on Ignition 8
safety concerns, if any, associated with its use. It is the
Silica 9
responsibility of the user of this standard to establish appro-
Iron, Aluminum, and Titanium Oxides 10
Iron Oxide 11 priate safety and health practices and determine the applica-
Titania 12
bility of regulatory limitations prior to use.
Alumina 13
Lime 14
2. Referenced Documents
Magnesia 15
Alkalies 16
2.1 ASTM Standards:
NOTE 1—These test methods have been compiled as standard proce- C322 Practice for Sampling Ceramic Whiteware Clays
dures for use in referee analyses. These test methods, however, when the
E11 SpecificationforWovenWireTestSieveClothandTest
determination of iron oxide as Fe O is involved, are not intended to
2 3
Sieves
preclude the use of other procedures that give results within the permis-
sible variations. For the sake of uniformity the classical Zimmerman-
3. Reagents
Reinhardt procedure is specified for the determination of iron oxide. It is
3.1 Unless otherwise indicated, it is intended that all re-
recognized that numerous other procedures are equally accurate and often
agents shall conform to the specifications of the Committee on
more convenient. The other procedures commonly in use include reduc-
tion of an oxidized solution with zinc or other metal, and titration with Analytical Reagents of theAmerican Chemical Society, where
standard potassium permanganate (KMnO ) or potassium dichromate
such specifications are available. Other grades may be used,
(K Cr O )solution,aswellastitrationwithastandardsolutionoftitanous
2 2 7 provided it is first ascertained that the reagent is of sufficiently
chloride in an oxidized solution. These procedures shall be considered
high purity to permit its use without lessening the accuracy of
acceptable, provided the analyst has obtained results by his special
the determination. Unless otherwise indicated, references to
procedurethatcheckwiththeZimmerman-Reinhardtprocedurewithinthe
water shall be understood to mean distilled water. Paragraphs
limits specified in Section 17. It is suggested that National Institute of
3.1.1-3.1.16 include those reagents common to two or more of
Standards and Technology standard samples be used for checking the
accuracy of procedures. the analytical procedures. Other reagents will be found listed
It will be understood that the making of a complete analysis of a
with the particular test method in which they are prescribed.
ceramic whiteware clay is a difficult procedure requiring a wide knowl-
3.1.1 Concentrated Acids and Ammonium Hydroxide—
edge of the chemistry involved in the operations and a thorough training
Concentrated acids and ammonium hydroxide of approxi-
in carrying out the work. A skilled analyst of good training is therefore
mately the following specific gravities or concentrations will
required to do the work.The descriptions here given cover the vital points
be required:
of procedure, but frequent reference in regard to the details of the various
manipulations should be made to “Applied Inorganic Analysis” by
Hillebrand and Lundell and to similar publications. Particularly in the 3
Blum, W., “Determination of Alumina as Oxide,” National Bureau of Stan-
dards, Scientific Paper No. 286.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
These test methods are under the jurisdiction of ASTM Committee C21 on Standards volume information, refer to the standard’s Document Summary page on
Ceramic Whitewares and Related Products and are the direct responsibility of the ASTM website.
Subcommittee C 21.04 on Raw Materials. Reagent Chemicals, American Chemical Society Specifications, American
Current edition approved Feb. 15, 2006. Published February 2006. Originally Chemical Society, Washington, DC. For suggestions on the testing of reagents not
approved in 1956. Last previous edition approved in 1999 as C323 - 56 (1999). listed by the American Chemical Society, see Analar Standards for Laboratory
DOI: 10.1520/C0323-56R06. Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
Hillebrand,W. F., and Lundell, G. E. F., Applied Inorganic Analysis,Wiley and
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
Son, New York, 1929.
MD.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
C323–56 (2006)
asbestos mat, porous glass, or porcelain filter, and keep in a
Hydrochloric acid (HCl) 1.19 sp gr
Nitric acid (HNO ) 1.42spgr
dark place. Standardize against the National Institute of Stan-
Sulfuric acid (H SO ) 1.84spgr
2 4
dards and Technology standard Sample No. 40c of sodium
Hydrofluoric acid (HF) 40 %
A
oxalate.
Perchloric acid (HClO ) 60to70%,cp
B
Sulfurous acid (H SO ) 6 % solution
2 3 3.1.14 Sodium Arsenite, Standard Solution— Dissolve
Ammonium hydroxide (NH OH) 0.90 sp gr
0.908 g of arsenious oxide, (As O ), in a small amount of hot
2 3
___________
sodium carbonate (Na CO ) solution, cool, filter, and dilute to
2 3
A
Lower purity varieties may contain aluminum oxide, (Al O ), as an impurity.
2 3
1 L. Standardize against a steel of known manganese content.
B
As supplied by reagent manufacturers.
3.1.15 Stannous Chloride Solution (50 g/L)—Dissolve 50 g
3.1.2 Diluted Acids and Ammonium Hydroxide—The di-
of SnCl in 100 mLof HCl and dilute to 1000 mL. Keep a few
lutedacidsandammoniumhydroxidereferredtoareofvarying
pieces of metallic tin in the bottle.
percentages by volume. They shall be made up by mixing
3.1.16 Titania, Standard Solution—Weigh out 0.05 g of
proportional volumes of the concentrated reagent and water.
calcined titanium dioxide (TiO ). Fuse with 10 g of K S O in
2 2 2 7
The diluted sulfuric acid mixtures shall be made up by slowly
a clean platinum crucible, keeping the temperature as low as
stirring the acid into the water. These diluted acids and
possible to maintain fluidity. Cool, and dissolve in about 300
ammoniumhydroxidearedesignatedinthemethodsas(1 + 4),
mL of H SO (1 + 5). Cool, transfer to a 500-mL volumetric
2 4
(1 + 9), and so forth, except very diluted solutions which are
flask, dilute to the mark with water, and mix thoroughly. To
referred to by the percent of reagent added. The designation in
standardize the solution, take two 50-mL portions in 400-mL
parentheses indicates the ratio of the volume of the concen-
beakers, dilute, boil, and precipitate with NH OH. Filter, and
trated reagent to the volume of water; for example, H SO
2 4
wash with hot water. Place the papers in the original beakers,
(1 + 9) contains 10 volume % of H SO (sp gr 1.84). The
2 4
add 15 mL of HCl, stir to macerate the paper, dilute, and
following will be required:
precipitate again with NH OH. Filter, and wash with hot water
Volume %
untilfreeofalkalisalts.Ignitecarefully,blast,andweigh.From
HCl 50
the weight determined, calculate the strength of the solution.
H SO 50
2 4
4. Sampling
HNO 30
4.1 Selection of Sample—Obtain the sample in accordance
with Practice C322.
NH OH 50
4.2 Crushthesampleinasmalljaworroll-typecrusherwith
hardenedtool-steelfacestopassa2.36-mm(No.8)sieve(Note
3.1.3 Ammonium Chloride (2 %)—Dissolve2gofNH Cl
2). Crush the sample to pass a 850-µm (No. 20) sieve, mix, and
in 100 mL of water.
quarter to about 50 g. Grind this 50-g sample so that it will all
3.1.4 Ammonium Oxalate Solution (Saturated)—Dissolve 4
pass a 150-µm (No. 100) sieve, unless otherwise specified, mix
gof(NH ) C O in 100 mL of water.
4 2 2
thoroughly, and place in a container that will ensure freedom
3.1.5 Chloroplatinic Acid Solution (10 %).
from contamination. Do fine grinding in a suitable mortar
3.1.6 Diammonium Phosphate Solution—Dissolve 10 g of
(agate, mullite, alumina, or boron carbide) to prevent the
(NH ) HPO in 100 mL of water.
4 2 4
introduction of impurities. Take precautions to prevent con-
3.1.7 Ethyl Alcohol (80 %)—Prepare a solution containing
tamination of the sample by steel particles from the sampling
80 volume % of ethyl alcohol in water.
equipment during crushing or grinding.
3.1.8 Ethyl Alcohol (Absolute)—Certain commercial brands
of denatured absolute alcohol are satisfactory as well as being NOTE 2—Detailed requirements for these sieves are given in Specifi-
cation E11.
considerably less expensive than the reagent grade absolute
alcohol.
5. Method of Analysis
3.1.9 Hydrogen Peroxide (30 %) (H O ).
2 2
5.1 Determine moisture on the sample in its ordinary
3.1.10 Manganese Sulfate Solution—Dissolve 70 g of crys-
air-dried condition. Determine all other percentage composi-
talline MnSO in 500 mLof water.Add 140 mLof phosphoric
tions on moisture-free samples and report accordingly on a
acid (H PO , sp gr 1.7), and 130 mL of sulfuric acid (H SO ,
3 4 2 4
moisture-free basis. The drying temperature recommended for
sp gr 1.84). Dilute to 1 L.
all moisture determinations is 105 to 110°C. Whenever a
3.1.11 Mercuric Chloride Solution (Saturated)—Prepare a
sample is weighed out for any determination other than
saturated solution of HgCl .
moisture,itshallbemoisture-free.Ifpreferred,thesamplemay
3.1.12 Potassium Permanganate, Standard
be dried in a weighing bottle from which the required samples
Solution (0.1N)—Dissolve 3.25 g of KMnO in 1000 mL of
shall be weighed out.
water. Allow to stand for one week, filter through an asbestos
mat, porous glass, or porcelain filter, and keep in a dark place.
6. Blank Determinations
Standardize against the National Institute of Standards and
Technology standard Sample No. 40c of sodium oxalate.
6.1 Make blank determinations on the reagents for each
3.1.13 Potassium Permanganate, Standard constituent in the whiteware clay and deduct this blank in each
Solution (0.04N)—Dissolve 2.5 g of KMnO in water and case. For the determination of the silica (SiO ) blank, approxi-
4 2
make up to 2 L.Allow to stand for one week, filter through an mately 0.25 g ofAl O should be added as aluminum chloride.
2 3
C323–56 (2006)
7. Moisture of 0.1 % methyl red solution. Heat the solution almost to
boiling, and add slowly NH OH (1 + 1) until the indicator has
7.1 Weigh 1.00 g of the sample and heat to constant weight
changed to a yellow color. Boil for several minutes to remove
at a temperature not under 105 nor over 110°C. Record the loss
the excess ammonia. Allow to settle for 30 min and decant
in weight as moisture.
through an open, rapid-filtering acid-washed filter paper, trans-
ferring the precipitate to the paper and washing the beaker and
8. Loss on Ignition
paper several times with a warm 2 % NH Cl solution. Reserve
8.1 Weigh 1.000 g of the moisture-free (105 to 110°C)
the filtrate, “A,” for the determination of calcium oxide (CaO)
sample and heat to constant weight over a blast lamp, or in an
and magnesium oxide (MgO) (Section 14). Return the precipi-
electric muffle furnace, at 900 to 1000°C. Record the loss in
tate and paper to the original beaker, add 50 mL of hot water
weight as the ignition loss.
and 10 mL of HCl (sp gr 1.19). Stir until the precipitate is
dissolved and the paper is well macerated. Dilute to about 200
9. Silica
mL with hot water, precipitate and filter as before. Combine
9.1 Weigh 0.5000 g of the moisture-free (105 to 110°C)
this filtrate “B” with filtrate“ A.” Wash the paper and precipi-
sample into a platinum crucible containing about5gof
tate with a warm 2 % NH Cl solution. Place the precipitate in
powdered anhydrous Na CO and mix well with a platinum
2 3 a weighed platinum crucible and ignite. Continue the ignition
wire. Cover the mixture with a little more Na CO . Heat
2 3
at 1200°C to constant weight (15 to 20 min is usually
gradually to the full heat of a good burner (1000 to 1100°C)
sufficient). Cool in a desiccator, and weigh with the crucible
maintained for about 1 h until complete solution is obtained.
covered with the lid.The R O consists of the aluminum oxide
2 3
Place the crucible cover on a triangle, and when the melt has
(Al O ), TiO , and Fe O present in the sample. In addition,
2 3 2 2 3
partially cooled, pour it on the lid (Note 3). When cool, place
there may be small amounts of phosphoric anhydride (P O ),
2 5
the crucible and lid in a 150-mL beaker, placing the button on
zirconium oxide (ZrO ), vanadium pentoxide (V O ), and
2 2 5
a watch glass above the beaker. Add 30 mL of HCl (1 + 1).
chromic oxide (Cr O ).
2 3
When solution is complete wash off the crucible and lid with
HCl (1 + 4), taking care to remove all SiO . Place the button in
11. Iron Oxide
the solution. Transfer the contents of the beaker to an evapo-
11.1 Procedure A: Fe O Determined on R O Sample—
2 3 2 3
rating dish and evaporate to dryness on a steam bath. Bake for
Heat the R O precipitate (Note 4) obtained in the determina-
2 3
1hat110°C.Add20to30mLofHCl(1 + 1)and50mLofhot
tion of iron, aluminum, and titanium oxides (Section 10), with
water. When all salts have been dissolved, allow to settle for
fused K S O or Na S O until solution is complete. Dissolve
2 2 7 2 2 7
several minutes and then filter through a general-purpose grade
the fusion in 50 mL of H SO (1 + 9) and evaporate to fumes.
2 4
acid-washed medium-retention filter paper. Wash the SiO
Cool, dilute with water, and filter off the SiO , washing with
three times by decantation using 20- to 30-mL portions of first
hot water. Reserve the filtrate for the determination of Fe O
2 3
hot water, then HCl (1 + 1), then hot water again. Transfer the
and TiO . Ignite the SiO in a platinum crucible and weigh.
2 2
precipitate to the filter paper, removing all SiO from the dish
Treat the precipitate with 5 mL of HF and two or three drops
with a policeman. Wash the paper and precipitat
...