ISO NP

Magnesium and magnesium alloys – Determination of beryllium

1 Scope

This standard specifies the methods for determination of beryllium in magnesium and magnesium
alloys according to the inductively coupled plasma atomic emission spectrometric methods
(hereafter, referred to as the "ICP atomic emission spectrometric method") and the atomic
absorption spectrometry.

2 Normative references

(It creates when proposing WD-draft.)

3 Terms and definitions

(It creates when proposing WD-draft.)

4 Classification of determination methods

The determination method of beryllium content shall be in accordance with one of the following.

a) ICP atomic emission spectrometric (Method A)

This method is applicable to magnesium of 0.00005 %(mass fraction) or over up to and including 0.001 %
(mass fraction) in beryllium content.

b) ICP atomic emission spectrometric (Method B)

This method is applicable to magnesium alloy of 0.00005 %(mass fraction) or over up to and including
0.002 % (mass fraction) in beryllium content

c) Atomic absorption method

This method is applicable to magnesium alloy of 0.001 % (mass fraction) or over in beryllium content.

5 Sampling, storing and weighing of analytical sample

5.1 Sampling method

The sampling method shall be as follows.

a) When the chips are sampled from a casting sample or a product sample, generally select more than one
sampling position and penetrate the sample by boring at right angles to its surface. In the case of a sample
with a thickness not penetrable from one direction, other suitable method (e.g.boring from two directions)
shall be used.

b) Prior to boring to obtain chips sample, clean the drill (not more than 10 mm in diameter) by using ethanol,
etc. Remove the adhered matters on the surface of the sampling position, then carry out the boring, not
using any sort of oils or lubricant, with just enough force to drill. At this time, adjust the pressure exerted or

1
ISO NP

the revolution frecuency of the drill so that no excessive heat is generated. Do not pour water or the like to
cool for the purpose of preventing the temperature rise.

Use of other cutting tools than a drill is permissible.

c) Collect all of the sample chips, the size of which shall not be more than 10 mm, and remove iron powder,
etc. by using a strong magnet. Then, mix them together well to take them as the analytical sample and
leave them in a desiccator to cool to room temperature.

d) If the sampling from thin sheets, pipes, etc. cannot be in accordance with specifications in a) to c), the
sampling method shall be subjected to the agreement between the purchaser and the supplier.

5.2 Storing of analytical sample

The storing of analytical sample shall be as follows

a) Store the analytical in a glass container with a lid, etc., sealed hermetically to prevent contamination.

b) Clean the analytical sample, when there is the possibility that oil and the like are adhered on the surface, by
using ethanol, acetone, etc., and dry it beforehand.

5.3 Weighing of analytical sample

The weighing of analytical sample shall be as follows.

a) In weighing out the analytical sample, mix the sample well so that any portion weighed out represents the
average composition.

b) Weigh out the analytical sample to the nearest 1 mg by using a chemical balance, etc.

6 ICP atomic emission spectrometric method (Method A)

6.1 Summary

The magnesium sample is decomposed with hydrochloric acid and nitric acid, then the solution is sprayed in
the argon plasma of ICP atomic emission spectrometer and the emission intensity is measured.

6.2 Reagents

The reagents shall be as follows.

6.2.1 Hydrochloric acid (1+1)

6.2.2 Nitric acid (1+1)

6.2.3 Magnesium solution (Mg : 40 mg/ml) Weigh out 33.2 g of magnesium oxide [not less than 99.99 %
(mass fraction)] and transfer it into a beaker (500 ml). Cover it with a watch glass, add 50 ml of water, then
add 288 ml of nitric acid (1+1) little by little to decompose it. After the reaction has quieted down, decompose
it completely by heating. After cooling it down to the ordinary temperature, wash the lower surface of the
watch glass and the inner wall of the beaker with water, remove the watch glass, transfer it into a 500 ml
volumetric flask by using water, and dilute it up to the mark with water.

6.2.4 Beryllium standard solution (Be : 5 µm/ml) Weigh out 0.125 g of beryllium [not less than 99.5 %
(mass fraction)], transfer it into a beaker (200 ml) and cover it with a watch glass. Add 40 ml of nitric acid
(1+1) to decompose it by gently heating. After cooling it down to the ordinary temperature, wash the lower
surface of the watch glass and the inner wall of the beaker with water, remove the watch glass and transfer it

2
 ISO NP

into a 500 ml volumetric flask by using water. Dilute it up the mark with water, and take it as the stock solution
(Be : 250 µg/ml). For each time of use, transfer 5.0 ml of this solution into a 250 ml volumetric flask, add 20 ml
of nitric acid (1+1), dilute it up to the mark with water, add take it as the beryllium standard solution.

6.3 Amount of sample to be weighed out

The amount of sample to be weighed out shall be 1.00 g and be weighed to the nearest 1 mg.

6.4 Operation

6.4.1 Preparation of sample solution

The preparation of sample solution shall be carried out according to the following procedures.

a) Weigh out the sample, transfer it into a beaker (300 ml), and cover it with a watch glass. Decompose it by
adding 10 ml of water and approximately 1 ml of nitric acid (1+1), and leave it as until the reaction quiets
down.

b) Decompose the solution by adding gradually 16 ml of nitric acid (1+1), approximately 2 ml at a time, and leave it as it is
until the reaction quiets down.

c) Add 1 ml of hydrochloric acid (1+1) to the solution, heat it on a hot plate at approximately 180 ℃ for 10 min
to 15 min, and decompose the sample completely.

d) After cooling it down to the ordinary temperature, wash the lower surface of the watch glass and the inner
wall of the beaker with water, and remove the watch glass. When undecomposed matter is present, filter it
with filter paper (Grade 5B), flake, and dilute it up to the mark with water.

6.4.2 Measurement of emission intensity

Spray a portion of the solution obtained in 6.4.1 d) in the argon plasma of ICP atomic emission spectrometer,
and measure the emission intensity of beryllium at wavelength Ⅱ (iron line) of 313.042 nm or 313.107 nm, or
at wavelength I (atomic line) of 234.861 nm.

6.5 Blank test

Take 25.0 ml of magnesium solution (6.2.3) in a beaker (300 ml), and carry out the same operation as that of
the sample on it according to the procedures in 6.4.1 b) to 6.4.2 in parallel with the operation on the sample.

6.6 Preparation of working curve

The preparation of working curve shall be carried out according to the following procedures.

a) Take 25.0 ml of magnesium solution (6.2.3), 2.0 ml of nitric acid (1+1) and 1.0 ml of hydrochloric acid (1+1)
in each of three separate 50 ml volumetric flasks, add stepwise 0ml, 1.0 ml and 2.0 ml (0µg, 5µg and 10µg
as the amount of beryllium) of beryllium standard solution (6.2.4), and dilute it ay up to the mark with water.

b) Spray a portion of the solution in the argon plasma of ICP atomic emission spectrometer, and measure the
emission intensity of beryllium at wavelength Ⅱ (ionic line) of 313.042 nm or 313.107 nm, or at
wavelength Ⅰ (atomic line) of 234.861 nm in parallel with the sample solution. Prepare the relation curve
between the emission intensity and the amount of beryllium added as the beryllium standard solution
(6.2.4). Translate the relation curve so that it passes through the origin, and take it as the working curve.

3
ISO NP

6.7 Calculation

Obtain the amount of beryllium from the emission intensity obtained in 6.4.2 and 6.5 and the working curve
prepared in 6.6, and calculate the content of beryllium in the sample according to formula (1).

A1 – A2
Be = m × 100 ……………………(1)

Where, Be: content of beryllium in sample [% (mass fraction)]

A1: amount or beryllium detected in sample solution (g)
A2: amount or beryllium detected in blank solution (g)
m: amount of sample weighed out (g)

7 ICP atomic emission spectrometric method (Method B)

7.1 Summary

After the magnesium alloy sample is decomposed with nitric acid, the solution is sprayed in the argon plasma
of ICP atomic emission spectrometer and the emission intensity is measured.

7.2 Reagents

The reagents shall be as follows.

4
 ISO NP

7.2.1 Hydrochloric acid (1+1)

7.2.2 Nitric acid (1+1)

7.2.3 Sulfuric acid (1+1)

7.2.4 Magnesium solution (Mg : 40 mg/ml ) Prepare in accordance with 6.2.3.

7.2.5 Aluminium solution (Al : 10 mg/ml ) Weigh out 2.0 g of aluminium [not less than 99.99 % (mass
fraction)], transfer it into a beaker (300 ml) and cover it with a watch glass. After adding 10 ml of water,
decompose it while adding the solution preliminary prepared by mixing 10 ml of hydrochloric acid (1+1) and 50
ml of nitric acid (1+1) little by little. When the reaction has quieted down, decompose it completely by heating.
After cooling it down to the ordinary temperature, wash the lower surface of the watch glass and the inner wall
of the beaker with water, remove the watch glass, transfer it into a 200 ml volumetric flask with water, and
dilute it up to the mark with water.

7.2.6 Zinc solution (Zn : 5.0 mg/ml) Weigh out 1.0 g of zinc [not less than 99.99 % (mass fraction)],
transfer it into a beaker (300 ml) and cover it with a watch glass. After adding 10 ml of water, decompose zinc
by adding 25 ml of nitric acid (1+1) little by little. When the reaction has quieted down, decompose it
completely by heating. After cooling it down to the ordinary temperature, wash the lower surface of the watch
glass and the inner wall of the beaker with water, remove the watch glass, transfer it into a 200 ml volumetric
flask with water, and dilute up to the mark with water.

7.2.7 Manganese solution (Mn : 2.0 mg/ml) Weigh out 0.50 g of manganese [not less than 99.95 % (mass
fraction)], transfer it into a beaker (300 ml) and cover it with a watch glass. After adding 10 ml of water, add 25
ml of nitric acid (1+1) little by little, and decompose it completely by heating. After cooling it down to the
ordinary temperature, wash the lower surface of the watch glass and the inner wall of the beaker, remove the
watch glass, transfer it into a 250 ml volumetric flask by using water and dilute it up to the mark with water.

7.2.8 Calcium solution (Ca : 1.0 mg/ml) Weigh out 0.499 g of calcium carbonate [not less than 99.99 %
(mass fraction)], transfer it into a beaker (300 ml) and cover it with a watch glass. After adding 10 ml of water,
decompose it completely by heating it while adding 10 ml of nitric acid (1+1), little by little. After cooling it
down to the ordinary temperature, wash the lower surface of the watch glass and the inner wall of the beaker
with water, remove the watch glass, transfer it into a 200 ml volumetric flask with water, and dilute it up to the
mak with water.

7.2.9 Copper solution (Cu : 1.0 mg/ml) Weigh out 0.20 g of copper [not less than 99.99 % (mass fraction)],
transfer it into a beaker (300 ml) and cover it with a watch glass. After adding 10 ml of water, add 10 ml of
nitric acid (1+1). Decompose it by heating gently. After cooling it down to the ordinary temperature, wash the
lower surface of the watch glass and the inner wall of the beaker with water, remove the watch glass, transfer
it into a 200 ml volumetric flask by using water, and dilute it up to the mark with water.

7.2.10 Silver solution (Ag : 4.0 mg/ml) Weigh out 0.80 g of silver [not less than 99.9 % (mass fraction)],
transfer it into a beaker (300 ml) and cover it with a watch glass. After adding 10 ml of water, add 15 ml of
nitric acid (1+1). Decompose it by heating gently. After cooling it down to the ordinary temperature, wash the
lower surface of the watch glass and the inner wall of the beaker with water, remove the watch glass, transfer
it into a 200 ml volumetric flask by using water, and dilute it up to the mark with water.

7.2.11 Zirconium solution (Zr : 1.0 mg/ml) Weigh out 0.338 g of zirconium oxide [not less than 99.9 %
(mass fraction)], which has been ignited to constant mass beforehand, transfer it into a beaker (200 ml) and
cover it with a watch glass. Add 10 ml of sulfuric acid and 10 g of ammonium sulphate, and heat it until it is
completely decomposed. After cooling it down to the ordinary temperature, add 15 ml of surfuric acid (1+1),
and make approximately 100 ml with water. Wash the lower surface of the watch glass and the inner wall of
the beaker with water, remove the watch glass, transfer it into a 250 ml volumetric flask by using water, and
dilute it up to the mark with water.

5
ISO NP

7.2.12 Strontium solution (Sr : 1.0 mg/ml) Weigh out 0.337 g of strontium carbonate [not less than
99.99 % (mass fraction)], transfer it into a beaker (300 ml) and cover it with a watch glass. After adding 10 ml
of water, add 10 ml of nitric acid (1+1) little by little, and decompose it completely by heating. After cooling it
down to the ordinary temperature, wash the lower surface of the watch glass and the inner wall of the beaker
with water, remove the watch glass, transfer it into a 200 ml volumetric flask by using water, and dilute it up to
the mark with water.

7.2.13 Lithium solution (Li : 1.0 mg/ml) Weigh out 1.99 g of lithium nitrate [not less than 99.9 % (mass
fraction)], transfer it into a beaker (300 ml) and cover it with a watch glass. After adding 10 ml of water, add 10
ml of nitric acid (1+1) little by little, and decompose it completely by heating. After cooling it down to the
ordinary temperature, wash the lower surface of the watch glass and the inner wall of the beaker with water,
remove the watch glass, transfer it into a 200 ml volumetric flask by using water, and dilute it up to the mark
with water.

7.2.14 Solution of other elements When any element (except silicon and rare earth elements) of not less
than 0.25 % (mass fraction), which is not aluminium, zinc, manganese, calcium, copper, silver, zirconium,
strontium or lithium, is present in sample, prepare the nitrate solution of the concerned element of 1 mg/ml in
concentration by using the high purity product of the concerned element.

7.2.15 Beryllium standard solution (Be : 5.0 µg/ml) Prepare in accordance with 6.2.4

7.3 Amount of analytical sample to be weighed out

The amount of analytical sample to be weighed out shall be 1.00 g and be weighed to the nearest 1 mg.

7.4 Operation

7.4.1 Preparation of sample solution

The preparation of sample solution shall be carried out according to the following procedures.

a) Weigh out the sample, transfer it into a beaker (300 ml), and cover it with a watch glass. Decompose it by
adding 10 ml of water and approximately 1 ml of nitric acid (1+1), and leave it as it is until the reaction quiets
down.

b) Decompose the solution by adding gradually 16 ml of nitric acid (1+1), approximately 2 ml at a time, and
leave it as until the reaction quiets down. Heat it on a hot plate at approximately 180℃ for 10 min 15 min and
decompose the sample completely.

c) After cooling it down to the ordinary temperature, wash the lower surface of the watch glass and the inner
wall of the beaker with water, and remove the watch glass. When undecomposed matter is present, filter
paper, transfer it into a 50 ml volumetric flask by using water and dilute it up to the mark with water. When the
sample contains zirconium, add 0.4 ml of sulfuric acid (1+1) and dilute it up to the mark with water.

7.4.2 Measurement for emission intensity

Spray a portion of the solution obtained in 7.4.1 c) in the argon plasma of ICP atomic emission spectrometer
and measure the emission intensity of beryllium at wavelength Ⅱ (iron line) of 313.042 nm or 313.107 nm ,
or at wave length Ⅰ (atomic line) of 234.861 nm.

7.5 Blank test

Add magnesium solution (7.2.4), aluminium solution (7.2.5), zinc solution (7.2.6), manganese solution (7.2.7),
calcium solution (7.2.8), copper solution (7.2.9), silver solution (7.2.10), zirconium solution (7.2.11), strontium
solution (7.2.12), lithium solution (7.2.13) and solution of other elements (7.2.14) so that the major component

6
 ISO NP

concentration is same as that of the sample. Carry out the same operations as the sample according to the
procedures in 7.4.1 b) and 7.4.2, in parallel with the operation on the sample.

7.6 Preparation of working curve

The preparation of working curve shall be carried out according to the following procedures.

a) Take magnesium solution (7.2.4), aluminium solution (7.2.5), zinc solution (7.2.6), manganese solution
(7.2.7), calcium solution (7.2.8), copper solution (7.2.9), silver solution (7.2.10), zirconium solution (7.2.11),
strontium solution (7.2.12), lithium solution (7.2.13) and the solution of other elements (7.2.14) in each of three
50 ml volumetric flasks so that the amount of magnesium, aluminium, zinc, manganese, calcium, copper,
silver, zirconium, strontium, lithium and other elements are the same as that contained in the sample weighed
out in 7.3. Add 1.9 ml of nitric acid (1+1), and after adding stepwise 0 ml, 1.0ml and 2.0ml (0 µg, 5µg and 10
µg as the amount of beryllium) of the beryllium standard solution (7.2.15), dilute it to the mark with water.

b) Spray a portion of the solution in the argon plasma of ICP atomic emission spectrometer, and measure the
emission intensity of beryllium at wavelength Ⅱ (ionic line) at 313.042 nm or 313.107 nm, or at wavelength
Ⅰ (atomic line) of 234.861 nm in parallel with the sample solution. Prepare the relation curve between the
emission intensity and the amount of beryllium added as the beryllium standard solution (7.2.15). Translate
the relation curve so that it passes through the origin and take it as the working curve.

7.7 Calculation

Obtain the amount of beryllium form the emission intensity obtained in 7.4.2 and 7.5 and the working curve
prepared in 7.6, and calculate the content of beryllium in the sample according to formula (2).

A1 – A2
Be = m × 100 ……………………(2)

Where, Be: content of beryllium in sample [% (mass fraction)]

A1: amount or beryllium detected in sample solution (g)
A2: amount or beryllium detected in blank solution (g)
m: amount of sample weighed out (g)

8 Atomic absorption method

8.1 Summary

The magnesium alloy sample is decomposed with hydrochloric acid and hydrogen peroxide, then the
absorbance of beryllium is measured by using an atomic absorption spectrometer.

8.2 Reagents

The reagents shall be as follows.

8.2.1 Hydrochloric acid (1+1)

8.2.2 Hydrogen peroxide

8.2.3 Beryllium standard solution (Be : 5 µg/ml) Weigh out 0.125 g of beryllium [not less than 99.5 %
(mass fraction)], transfer it into a beaker (300 ml) and cover it with a watch glass. Add 50 ml of hydrochloric
acid (1+1) to decompose it by gently heating. After cooling it down to the ordinary temperature, wash the
lower surface of the watch glass and the inner wall of the beaker with water, remove the watch glass, and

7
ISO NP

transfer it into a 500 ml volumetric flask by using water. Dilute it up to the mark with water, and take it as the
stock solution (Be : 250 µg/ml). For each time of use, transfer 5.0 ml of this solution into a 250 ml volumetric
flask, add 20 ml of hydrochloric acid (1+1), dilute it up to the mark with water, and take it as the beryllium
standard solution.

8.2.4 Sulfuric acid (1+1)

8.3 Amount of sample to be weighed out

The amount of sample to be weighed out shall be 1.00 g and be weighed to the nearest 1 mg.

8.4 Operation

8.4.1 Preparation of sample solution

The preparation of sample solution shall be carried out according to the following procedures.

a) Weigh out the sample, transfer it into a beaker (300 ml), and cover it with a watch glass. Decompose it by
adding 10 ml of water and approximately 1 ml of hydrochloric acid (1+1), and leave it as it is until the reaction
quiets down.

b) Add gradually 29 ml of hydrochloric acid (1+1) to the solution to decompose. When the reaction quiets
down, add 1 ml of hydrogen peroxide, heat it on a hot plate at approximately 120 ℃ for 10 min to 15 min and
decompose the sample completely.

c) After cooling it, down to the ordinary temperature, wash the lower surface of the watch glass and the inner
wall of the beaker with water, and remove the watch glass. When undecomposed matter is present, filter
paper (Grade 5B), and wash it with water. Put the filtrate and the washings into a 100 ml volumetric flask by
using water and dilute it up to the mark with water. When the sample contains zirconium, add 0.4 ml of sulfuric
acid (1+1) and dilute it up to the mark with water.

8.4.2 Measurement of absorbance

Spray a part of the solution obtained from 8.4.1 c) into the acetylene-dinitrogen monoxide flame of atomic
absorption spectrometer, and measure the absorbance at 234.8 nm in wavelength by making a hollow
cathode lamp of beryllium the light source.

Correct the absorbance by carrying out the background correction based on any one of the background
correction system using continuous spectrum light source, Zeeman splitted spectrum, non-resonance
spectrum or self-reversal spectrum. In the background correction system using continuous spectrum light
source, use a deuterium lamp as the light source, measure the absorbance under the same condition in which
a hollow cathode lamp is made to be the light source and subtract the value from the absorbance when a
hollow cathode lamp is used as a light source, and take the value obtained as the absorbance the sample.

8.5 Blank test

The operations of blank test shall be as follws.

Add magnesium solution (7.2.4), aluminium solution (7.2.5), zinc solution (7.2.6), manganese solution (7.2.7),
calcium solution (7.2.8), copper solution (7.2.9), silver solution (7.2.10), zirconium solution (7.2.11), strontium
solution (7.2.12), lithium solution (7.2.13) and solution of other elements (7.2.14) in a beaker (300 ml) so that
the concentration of the main component becomes same as the sample. Then, carry out the same operation
as the sample in parallel to the sample according to the procedures of 8.4.1 b) ti 8.4.2.

8.6 Preparation of working curve

The preparation of working curve shall be in accordance with following procedures.

8
 ISO NP

a) Take magnesium solution (7.2.4), aluminium solution (7.2.5), zinc solution (7.2.6), manganese solution
(7.2.7), calcium solution (7.2.8), copper solution (7.2.9), silver solution (7.2.10), zirconium solution (7.2.11),
strontium solution (7.2.12), lithium solution (7.2.13) and solution of other elements (7.2.14) in three 50 ml
volumetric flasks respectively so that the amount of magnesium, aluminium, zinc, manganese, calcium,
copper, silver, zirconium, strontium, lithium and other elements are same as the amount contained in the
sample weighed out in 8.3, add 6 ml of hydrochloric acid (1+1), then add stepwise the beryllium standard
solution (7.2.15) of 0 ml, 5.0 ml and 10 ml (0 µg, 25µg and 50 µg as the amount of beryllium) and dilute them
the mark with water.

b) Spray a part of this solution into acetylene-dinitrogen monoxide flame of atomic absorption spectrometer,
and measure the absorbance at 234.8 nm in wavelength by making a hollow cathode lamp of beryllium the
light source. Carry out the background correction according to the procedures in 8.2.4, prepare the relation
line between the obtained absorbance after correction and the amount of beryllium added as the beryllium
standard solution (8.2.3). Translate the relation curve so that it passes through the origin and take it as the
working curve.

8.7 Calculation

Obtain the amount of beryllium form the absorbance obtained in 8.4.2 and 8.5, and the working curve
prepared in 8.6, and calculate the content of beryllium in the sample according to formula (3).

A1 – A2
Be = m × 100 ……………………(3)

Where, Be: content of beryllium in sample [% (mass fraction)]

A1: amount or beryllium detected in sample solution (g)
A2: amount or beryllium detected in blank solution (g)
m: amount of sample weighed out (g)