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TAPPI/ANSI T 419 om-18

OFFICIAL STANDARD – 1926


TENTATIVE STANDARD – 1960
OFFICIAL TEST METHOD – 1980
REVISED – 1985
REVISED – 1991
REVISED – 2002
REAFFIRMED – 2004
REAFFIRMED – 2009
REVISED – 2011
REVISED – 2018
2018 TAPPI

The information and data contained in this document were prepared by


a technical committee of the Association. The committee and the
Association assume no liability or responsibility in connection with the
use of such information or data, including but not limited to any
liability under patent, copyright, or trade secret laws. The user is
responsible for determining that this document is the most recent
edition published.

CAUTION:
This Test Method may include safety precautions which are believed to be appropriate at the time of publication of the method. The intent of these is
to alert the user of the method to safety issues related to such use. The user is responsible for determining that the safety precautions are complete and
are appropriate to their use of the method, and for ensuring that suitable safety practices have not changed since publication of the method. This
method may require the use, disposal, or both, of chemicals which may present serious health hazards to humans. Procedures for the handling of such
substances are set forth on Material Safety Data Sheets which must be developed by all manufacturers and importers of potentially hazardous
chemicals and maintained by all distributors of potentially hazardous chemicals. Prior to the use of this method, the user must determine whether any
of the chemicals to be used or disposed of are potentially hazardous and, if so, must follow strictly the procedures specified by both the manufacturer,
as well as local, state, and federal authorities for safe use and disposal of these chemicals.

Starch in paper

1. Scope

1.1 This method describes the qualitative and the quantitative determination of unmodified starches and
starches modified only by conventional oxidation techniques or enzyme conversion, which are used for beater addition or
surface sizing.
1.2 This procedure measures the total starch content and does not differentiate between starch inside and on
the surfaces of the paper.
1.3 Some starches that are cationic, substituted, grafted, or combined with resins are not within the scope of
this procedure, because special techniques are required for them. Test to determine whether the starch is appropriate for
this procedure by checking for extractability. If it can be extracted quantitatively and forms the iodine complex, it should
be able to be determined by this method.
1.4 This method is applicable only for papers with fully bleached pulp, because lignin and lignin remnants
can also react with iodine to form a color complex.

2. Significance

The amount of actual starch content is a measure of the starch sizing content added to the paper. It can also be
used as a measure of wet end starch retention in the papermaking process.

3. Qualitative

3.1 Apparatus
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3.1.1 Glassware and other equipment: beakers, 50 and 150 mL; graduated cylinder, 100 mL; small filter
funnel; filter paper.

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3.2 Reagent
3.2.1 Iodine solution, about 0.001N I2. Make a 0.01N stock solution of iodine by dissolving 0.13 g I2 in a
solution of 2.6 g KI in 5 mL of water and diluting to 100 mL. Dilute one part of this with nine parts of water, to a pale
yellow color, each time a test for starch is made.
3.3 Test specimen. From each test unit of a sample obtained in accordance with TAPPI T 400 “Sampling and
Accepting a Single Lot of Paper, Paperboard, Containerboard, or Related Product,” weigh a representative specimen of
approximately 0.5 g and cut into pieces 5 to 10 mm square.
3.4 Procedure. Boil the paper specimen for several minutes with 10 mL of water. Filter, cool the filtrate, and
add one drop of the dilute I solution. A blue coloration indicates starch. A faint violet coloration should be disregarded,
2

as nonstarch constituents of paper sometime give this reaction.

4. Quantitative

4.1 Apparatus
4.1.1 Disintegrator, for disintegrating the specimen in water. A domestic high-speed electric mixer is
preferable, but any other means, e.g., glass beads and bottle, may be used.
4.1.2 Fritted glass filter funnels, coarse, about 50 mL or larger, or Büchner funnels and general purpose ashless
filter paper with medium speed and retention, other equivalent acid washed filter paper, or glass microfiber filters. When
using fritted glass filters, clean by passing 5N NaOH through the filter and washing once with hot water. If this does not
remove all starch residue, heat the frit in a 480ºC furnace in an oxidizing atmosphere.
4.1.3 Filtration flask, 500 mL or larger.
4.1.4 Centrifuge, preferably with a capacity of over 50 mL.
4.1.5 Spectrophotometer, for absorption measurements at 580 nm. Either a double beam spectrophotomer or a
filter comparator may be used. In either case, use the same instrument and conditions for a calibration curve as for the
specimen.
4.1.6 Other equipment, 50, 100, and 500 mL volumetric flasks; 25 and 2.5 mL pipets; 250 mL beaker; boiling
water or steam bath, stopwatch.
4.1.7 Hood, for use in carrying out extractions with HCl. A standard laboratory fume hood is adequate to
protect personnel and laboratory environment from the effects of HCl fumes.
4.1.8 Glassware for this procedure must be scrupulously clean. The laboratory can verify this by
running a blank with cotton linters through the entire section 4.4 procedure. If residual starch is found, the
laboratory should modify its glassware cleaning procedures. For example, after cleaning glassware can be heated
in a muffle furnace for 1-2 hours at 425°C to destroy any remaining traces of starch.
4.2 Reagents
4.2.1 Hydrochloric acid, concentrated HCl, also solutions diluted 1 + 1 (approximately 6N), 1 + 9 (approx.
1.2N) and 1 + 19 (approx. 0.6N).
4.2.2 Potassium iodide-iodine reagent, 7.5 g KI and 5 g I2 per liter. Dissolve 7.5 g KI in 10 mL of water, add 5
g I2. Dilute to 1 L after iodine is dissolved.
4.2.3 Cotton linters.
4.2.4 Reagent grade deionized water, meeting ASTM D1193, Type II specifications.
4.3 Test specimens. From each test unit of a sample obtained in accordance with TAPPI T 400 “Sampling and
Accepting a Single Lot of Paper, Paperboard, Containerboard, or Related Product,” weigh to the nearest 5 mg, two 1-g
representative specimens consisting of small (5 to 10 mm) strips. Do not dry-grind the paper, since it may lose some of its
starch, especially if it contains a filler. At the same time, unless the moisture content is known to within 1%, weigh
another 1.0-g specimen for determining the moisture in accordance with TAPPI T 412 “Moisture in Paper and
Paperboard.”
4.4 Procedure
4.4.1 Transfer the first specimen to the disintegrator, disintegrate in 60 ± 20 mL of deionized warm water (40-
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80°C) and quantitatively transfer to a 250-mL beaker, using enough rinsing warm water to make the specimen up to 100
mL. If the sample seems to lack sufficient body to form a substantial pad, add some cotton linters (less than 1 g). Heat on
the bath to just below the boiling point for 15 minutes after temperature in the beaker reaches 92°C.
4.4.2 Transfer the contents of the beaker to the funnel on the filtration flask. Drain and wash the residue with
10-12 mL of hot deionized water. Remove suction from the flask. Cool to room temperature in an ice bath. Extract the

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pad with HCl, closely controlling the extraction times to prevent losses of starch by hydrolysis. For the first HCl
extraction, add 25 mL of the (1 + 1) HCl to the filter crucible, allow to stand for 3 minutes (preferably stir with a glass
rod to break up the pad) and apply the suction. Remove suction from the flask. Repeat the 3 minute extraction with 25
mL of the (1 + 1) HCl. Drain. Remove suction. Add 25 mL of concentrated HCl, break up pad and stir for 40 seconds.
Immediately quench the reaction by adding 50 mL of deionized water (20-25ºC) to the funnel. Reapply the suction and
swirl the flask so as to mix the concentrated HCl in the filtrate. Wash the residue 3-4 times with small volumes of water
(25 mL). Do not exceed 450 mL total volume in the flask. Test for complete removal of the starch by adding a drop or
two of the dilute iodine solution to the pad. Even a trace of residual starch will cause the appearance of a blue color. If
residual starch is found, transfer the pad back to the 250 mL beaker, add 100-150 mL water, and repeat starting at the
heating stage. If residual starch is still found after 2 extractions, discard and start over using a smaller, 0.5-gram
specimen. If complete starch extraction is still not achieved after two sets of extractions on a 0.5-gram specimen, report
the test results with a note stating that the starch could not be quantitatively extracted from the sample.
4.4.3 Transfer the starch solution to a 500-mL volumetric flask (1000 mL if a second set of HCl extractions
was done), cool to room temperature, and dilute to the mark with deionized water. Mix thoroughly and, if the solution is
turbid because of fillers or extraneous material, centrifuge approximately 50 mL for 10 minutes.
4.4.4 Pipet 25 mL of the clear supernatant liquid into a 50 mL volumetric flask, pipet 2.5 mL of the KI-I2 2

reagent into the flask, dilute to the mark, and mix thoroughly. If the paper is known to contain Kymene resin, to avoid
precipitating it halve the KI-I2 level by doubling the sample aliquot into a 100 mL volumetric flask while keeping the KI-
I2 reagent the same. Prepare a sample blank by pipeting 10 mL of the clear supernatant liquid into a test tube, add 10 mL
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deionized water and mix the solution. Prepare a blank solution by mixing 25 mL of (1 + 9) HCl with 2.5 mL of the KI-I2 2

reagent in a 50 mL volumetric flask and dilute to the mark. Mix thoroughly. Measure the absorbance of the blank, sample
blank, and sample solutions in 1 cm cells at 580 nm. If a reference beam is used with your instrument, use deionized
water or the blank solution in the reference beam. Make sure that steps 4.4.3 and 4.4.4 are completed within one hour
after the acid extractions, to avoid starch hydrolysis in the filtrate by the acid present. In addition, make sure that the
absorbance of the solution is measured within 30 minutes after the color complex is formed.

Note 1: A limitation of Beer's Law is that at high absorbance (> 1.0) the relationship between absorbance and
concentration of the light-absorbing species may no longer be linear, so that the absorptivity could change. Therefore if
the sample absorbance is greater than 1.0, a smaller aliquot such as 10 ml should be taken in step 4.4.4

4.4.5 Repeat for the second specimen.


4.4.6 A control sample of paper containing a known amount of starch should be run along with the specimen
determinations. The determined value should be within the target range of the control in order to report the specimen
data.
4.4.7 Calculations: %wt on an oven-dry basis.

A Vf 1
% starch = × V0 × ×
ab VA 10S

where A = net absorbance = A sample - A blank - A sample blank (If the blank solution was used in a double beam
spectrophotomer, then A blank drops out.)

a = starch absorptivity determined from calibration in liters/g-cm


b = cell pathlength in cm
V0 = volume in mL of starch solution after extraction, either 500 or 1000 mL
Vf = final volume in mL of starch solution where color is measured, normally 50 mL
VA = volume in mL of aliquot taken from V0, normally 25 mL
S = OD sample weight

4.4.7.1 Sample calculation:

A sample = 0.600
A blank = 0.060
A sample blank = 0.005

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A = 0.600 – 0.060 – 0.005 = 0.535


a = 12.50 liters/g-cm
b = 1 cm
Vo = 500 mL
Vf = 50 mL
Va = 25 mL
S = 1.0045 g OD

0.535 50 ml 1
% starch = × 500 mL x × = 4.26% OD
12.5 1/g-cm (1 cm) 25 ml 10 (1.0045 g OD)

4.5 Calibration curve


4.5.1 If possible, use the same starch that was added to the paper for preparing the calibration curve. Otherwise,
use a composite mixture of three or four common types of starches. (A value of 12.5 liters/g-cm is a fairly typical average
of common starches for the absorptivity that could be used for comparative results between a set of samples where the
type of starches used are unknown.) Weigh 0.1 g starch corrected for moisture and ash (the ash content of unmodified
starch usually can be neglected, while acid-modified starches, oxidized starches and starches containing borax contain 1
or 2% ash) into a 250 mL beaker, add 100 mL distilled water and heat for 15 min after the temperature in the beaker
reaches 92°C. Add 1.0 g cotton linters and heat for 15 minutes longer. Decant with suction through the coarse fritted
glass filter, wash the beaker once with hot water and refilter the water through the mat. Cool to room temperature in an
ice bath.
4.5.2 Proceed with the HCl and extraction treatments exactly as described for the paper specimen, diluting the
filtrate to 500 mL in a volumetric flask. Centrifuge a portion of this starch solution for 10 minutes and remove aliquots to
prepare the calibration curve. Keep all the concentrations and the period between forming the starch-iodine complex and
measuring its absorbance the same as for the specimen. A suggested dilution schedule is given in Table 1.

Table 1. Dilution procedure for preparing a calibration curve

Starch Total 0.2 g/L KI


concentration, volume, starch solution, Watera, solutionb,
g/L mL mL mL mL

0.010 100 5 0 5
0.020 100 10 5 5
0.030 100 15 10 5
0.040 100 20 15 5
0.050 100 25 20 5

Dilute to the mark in a volumetric flask with (1 + 19) HCl


aGraduated cylinder is sufficiently accurate.
bAdd this solution from a pipet or buret.

4.5.3 Calculate the actual final starch concentration of each calibration solution from the OD ash corrected
weight of starch used and the dilution. Plot the net absorbance versus the actual concentration. This plot should be linear
and pass through the origin. Determine the absorptivity a from the slope of the line.

A = abc

where

A = net absorbance as above


a = absorptivity of the starch in L/g-cm

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b = cell pathlength in cm
c = actual concentration in g/L
slope of line = ab

Calculate a and average the results or preferably run a least squares fit on the line and get a from the slope.
4.6 Report. Average the results of the two determinations and report the amount of starch as a percentage of
the moisture-free paper to the nearest 0.1%.
4.7 Precision. The following estimates of repeatability and reproducibility are based on data from an
interlaboratory study conducted in March 2002. All samples on which this data is based were uncoated printing and
writing grades. Participants were asked to follow TAPPI T 419 om-91 “Starch in Paper” (Quantitative), revision of this
method. Testing was based on two (2) determinations per test result and three (3) results per lab, per material. The
number of laboratories participating was limited. The user of this data is cautioned that the results could be more variable
with the limited values that if there were more participants in the study.

Repeatability, r (within a lab)


r = 0.38
%r = 7.7%

Reproducibility, R (between laboratories)


R = 1.88
%R = 35.8%

Repeatability and reproducibility are estimates of the maximum difference (at 95%) which should be expected when
comparing test results for materials similar to those described above under similar test conditions. These estimates may
not be valid for different materials or testing conditions.

Property Measured – Percent (%) Starch


Material Grand mean Repeatability Reproducibility Labs included
r and (%r) R and (%R)
S1 5.97 0.56 (9.37%) 2.77 (46.49%) 4 of 4
S2 5.95 0.38 (6.45%) 3.69 (62.13%) 4 of 4
S3 4.40 0.26 (5.90%) 0.70 (16.00%) 4 of 4
S4 4.48 0.36 (8.07%) 1.28 (28.51%) 4 of 4
S5 3.72 0.32 (8.56%) 0.96 (25.84%) 4 of 4

5. Keywords

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Starch, Paper, Quantitative analysis, Qualitative analysis

6. Additional information

6.1 Effective date of issue: April 17, 2018.


6.2 Calibration curves for the various starches being analyzed and exacting laboratory techniques are most
important. A reliable calibration curve prepared for starch avoids the need for subsequently preparing another calibration
curve.
6.3 In 1991, this method was revised to give proven results that are more consistent and reliable. In addition,
this methodology has been found to work with most of the starches on the market today.
6.4 The 2009 revision included a new repeatability and reproducibility precision statement.
6.5 In 2011, this method was revised to: allow test results to be reported (with a note) even if complete starch
extraction could not be achieved; eliminate the use of hazardous chromic acid cleaning solution; provide a more
representative value for the blank light absorbance in the sample calculation; eliminate the possibility of overnight
settling of turbid filtrates, and instead require centrifuging; require filtrates be analyzed within one hour to avoid acid
hydrolysis of the extracted starch; and limit the scope to papers with fully bleached pulp.

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6.6 Related methods: PAPTAC G.23. Please note that PAPTAC Standard Testing Methods and Useful
Methods are archival documents available for reference only as of October 1st, 2015.
6.7 For a list of references, see Tappi 51 (2): 167A (1968).

Your comments and suggestions on this procedure are earnestly requested and should be sent to the TAPPI Standards
Department. 

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