Decree No. 10 / 2006 Coll.
Decree amending Decree No. 164 / 2004 Coll., laying down basic methods for the testing of hazardous properties of chemicals and chemical preparations in terms of flammable and oxidative capacity
Valid
Effective from 12.01.2006
10
DECLARATION
of 27 December 2005
amending Decree No 164 / 2004 Coll., laying down the basic methods for testing the hazardous properties of chemicals and chemical preparations with regard to flammable and oxidative properties
The Ministry of the Interior provides pursuant to § 8 (5) (a) of Act No. 356 / 2003 Coll., on Chemicals and Chemical Products and amending certain laws:
Decree No. 164 / 2004 Coll., laying down the essential methods for testing the hazardous properties of chemicals and chemical preparations with regard to flammable and oxidative properties, is amended as follows:
1. In Paragraph 2 (1), at the end of point (g), the word "a 'is replaced by a comma.
2. In Article 2, at the end of paragraph 1, the dot is replaced by "a 'and the following point (i) is added:
"(i) oxidative properties of liquids."
3. In the Annex, point IX is added:
"IX. METHOD FOR THE DETERMINATION OF CAPALIN OXIDUAL PROPERTIES - Method A.21 of Annex 2A to Commission Directive 2004 / 73 / EC of 29 April 2004 adapting to technical progress for the 29th time Council Directive 67 / 548 / EEC on the approximation of laws, regulations and administrative provisions relating to the classification, packaging and labelling of dangerous substances
IX.1 INTRODUCTION
This method is used to determine the ability of a liquid to increase the rate or intensity of burning of a flammable substance or to form a mixture with a flammable substance that ignites spontaneously after careful mixing. This method requires comparison with only one reference substance.
Information shall be obtained before the test begins, unless the substance has explosive properties.
If there is clear evidence from the chemical structural formula of the substance or preparation that the substance or preparation is unable to react externally with the flammable material, no test shall be carried out.
The test is not intended for solids and preparations, gases, explosive or highly flammable substances and preparations and for organic peroxides.
IX.1.2 DEFINITION OF EXTERNAL TIME OF FACE AND UNIT
The average time of pressure rise (ms) means the arithmetic mean of the duration of the pressure increase from 690 kPa to 2,070 kPa above atmospheric pressure for the mixture under test conditions.
IX.1.3 REFERENCE LABEL FOR DETERMINATION OF OXIDUAL PROPERTIES
An aqueous solution of 65% hm. nitric acid (p.a.), the concentration of which is confirmed by titration before testing, shall be used as the reference substance. The test may also be performed with other reference substances, e.g. 50% hm chloride acid and 40% hm sodium chloride if the results are to be used for other purposes.
IX.1.4 PRINCIPLE OF METHODS
The test liquid is mixed with fibrous cellulose in a 1: 1 ratio and put into a pressure vessel. If spontaneous ignition occurs during mixing or filling, no further testing is necessary.
If spontaneous ignition does not occur, then continue as follows. The mixture shall be heated in a pressure vessel and the average time at which the pressure rises from 690 kPa to 2 070 kPa above atmospheric pressure shall be measured. This value shall be compared with the measured average rise in pressure of a mixture of reference substance (s) and cellulose prepared at a ratio of 1: 1.
IX.1.5 QUALITATIVE CRITERIA OF METHODS FOR DETERMINATION OF OXIDUAL PROPERTIES
In a series of five repeated tests with one substance, neither result should differ by more than 30% from the arithmetic mean. Results that differ from the arithmetic mean by more than 30% are excluded, the mixing and filling process is refined and the testing is repeated.
IX.1.6 PREPARATION, CONDITIONS AND IMPLEMENTATION OF THE TEST
IX.1.6.1. A dried fibrous cellulose with a fibre length of 50 μm to 250 μm and a mean diameter of 25 μm (e.g. a cellulose powder for column chromatography) shall be used as flammable material. Dry for 4 hours at 105 ° C in a layer of not more than 25 mm thick to a constant weight and kept in a desiccator above the dryer until cooling and further use. The drying period shall be selected in such a way that the moisture content of the dried cellulose is less than 0,5% (on a dry basis). For example, titration according to Karl-Fisher is confirmed.
This moisture content is also achieved by heating at 105 ° C in a vacuum for 24 hours. The same batch of cellulose shall be used for the whole test.
IX.1.6.2 The test shall be carried out using a pressure vessel made up of a steel cylinder of length 89 mm and an external diameter of 60 mm (Figure 5). The cylinder is worked on opposite sides into flat surfaces (50 mm cross-section of the container is in these places) to facilitate screw-in of the spark plugs and relief fuses. The container has an inside diameter of 20 mm and is extended to a depth of 19 mm inside at both ends and has a thread of 25.4 mm (1 "BSP- British Standard Pipe). At a distance of 35 mm from one straight end and at an angle of 90 °, the side arm for measuring pressure is bolted into the cylinder wall of the pressure vessel. The opening for this arm is drilled to a depth of 12 mm and equipped with a thread of 12,7 mm (1 / 2" BSP). The same thread is also on the side shoulder. If necessary, gas-tight shall be ensured by inert sealing. The side arm exceeds the body of the container by 55 mm and has a 6 mm diameter bore channel. It is drilled and threaded at the end of the side arm for the membrane pressure sensor. Any pressure gauge which is resistant to hot gases and decomposition products may be used and responds not later than 5 ms to the pressure increase from 690 kPa to 2 070 kPa.
The end of the pressure vessel further away from the side arm is equipped with a spark plug with two electrodes, one isolated from the body of the candle and the other grounded through the candle. The second end of the pressure vessel is closed by a burst disc (burst pressure of approximately 2,200 kPa), fixed by a relief fuse with a 20 mm bore. If necessary, the gas-tight spark plugs shall be secured by inert sealing. The stand (figure 6) holds the assembly in the correct position during use. It consists of a base, a plate of soft steel with dimensions 235 mm x 184 mm x 6 mm and a 185 mm hollow prism with dimensions 70 mm x 70 mm x 4 mm.
The lower end of the prism is cut out to form two opposite side supports (legs) which pass into an intact original profile of 86 mm long. The ends of these supports are cut at an angle of 60 ° to the horizontal plane and welded to the base. On one side of the upper end of the prism is a cut 22 mm wide and 46 mm deep, into which the side arm of the pressure vessel fits, after the pressure vessel is placed in the holder (ignition candle first). The inner lower side of the upper end of the prism holder is welded to a distance steel plate 30 mm wide and 6 mm thick. The pressure vessel is provided in the correct position by two screws with a 7 mm thread with wing nut placed in the openings on the opposite side. Two steel bands 12 mm wide and 6 mm thick, supporting the pressure vessel from the bottom, are made on the sides adjacent to the bottom of the intact profile of the prism holder.
IX.1.6.3 The ignition system contains Ni / Cr wire 25 cm in length, 0,6 mm in diameter and has a resistance of 3,85 kg.m-1. Wire with a 5 mm diameter bar into the shape of a coil and connect to the electrodes in the ignition candle. Two possible versions of the coil are shown in Figure 7. The distance between the lower side of the container and the ignition coil is 20 mm. If the electrode position is not adjustable, the ends of the ignition wire between the coil and the bottom of the pressure vessel shall be insulated by a ceramic casing. The wire is heated by an electrical source capable of delivering a constant current of at least 10 A.
IX.1.6.4 Exam. The device equipped with a pressure sensor and a heating system (without a discharge disc relief device) shall be placed in the stand by the ignition candle downwards. In the glass beaker, 2,5 g of the test liquid is mixed with 2,5 g of dried cellulose using the glass rod. A mixture of oxidiser and cellulose must be treated with due care (risk of explosion).
In practice, mixtures of test liquid and cellulose are prepared at a mass ratio of 1: 1 in excess of that required for the test. From it, the container shall then be placed (5 ± 0,1) g.
The operator prepares the mixture using a protective shield. If the mixture ignites during mixing or filling, the test shall not be continued. The mixture shall be added to the pressure vessel in small parts, and shall be checked by foot, ensuring that the mixture surrounds and is in close contact with the ignition coil. It is important that there is no deformation of the coil during the filling and that the adjacent coils are not touched. A burst disc is inserted into the pressure vessel and the relief fuse is screwed. The filled container shall be placed in the test bench with a burst disc upwards and the whole assembly placed in a suitable armoured digestor or in an explosive chamber. The external clamps of the ignition candle shall be connected to an electrical power supply of 10 A. From the start of mixing and connection to the current source shall not exceed 10 minutes.
The pressure sensor signal shall be recorded by a system that allows both evaluation and continuous recording of the time course of pressure (e.g. a transverse event recorder with a paper record). The mixture shall be heated until the burst disc breaks or for 60 seconds. If the burst disc does not break, before the device is dismantled, allow the mixture to cool off and be carefully pressurised. Five experiments with the test substance and the reference substance (s) shall be carried out. Time at which pressure rises from 690 kPa to 2,070 kPa above atmospheric pressure shall be recorded and the mean shall be calculated from them.
In some cases substances may generate pressure increases too large or too small due to chemical reactions that do not characterise the oxidative properties of the substance. It is then necessary to repeat the test with an inert substance such as quartz (infusory earth) instead of cellulose to clarify the nature of this reaction.
IX.2 DATA FOR EVALUATION OF TEST RESULTS
Time of pressure rise for both the test substance and the reference substance (s).
Time of pressure rise from inert test (if performed).
IX.3 PROCESSING OF RESULTS
The average time of pressure rise for both the test substance and the reference substance (s) shall be calculated.
Calculate the average pressure increase time from the inert test (if performed).
Examples of results are shown in Table 1.
IX. 4 COMMUNICATION OF RESULTS
The test report shall contain the following information:
(a) identification, composition, purity, etc. of the test substance or preparation;
(b) the concentration of the test substance or preparation;
(c) the drying process of the cellulose used;
(d) the moisture content of the cellulose used,
(e) the results of the measurements;
(f) test results with an inert substance (if any);
(g) calculated average times of pressure rise;
(h) any deviations from and reasons for this method;
(i) any other data or notes relevant to the interpretation of the results.
Table 1
| Příklady výsledků | |
|---|---|
| Látkac | Průměrná doba nárůstu tlaku (ms) u směsí s celulosou v poměru 1:1 |
| Dichroman amonný, nasycený vodný roztok | 20 800 |
| Dusičnan vápenatý, nasycený vodný roztok | 6 700 |
| Dusičnan železitý, nasycený vodný roztok | 4 133 |
| Chloristan lithný, nasycený vodný roztok | 1 686 |
| Chloristan hořečnatý, nasycený vodný roztok | 777 |
| Dusičnan nikelnatý, nasycený vodný roztok | 6 250 |
| Kyselina dusičná, 65% | 4 767a |
| Kyselina chloristá, 50% | 121a |
| Kyselina chloristá, 55 % | 59 |
| Dusičnan draselný, 30% vodný roztok | 26 690 |
| Dusičnan stříbrný, nasycený vodný roztok | — b |
| Chlorečnan sodný, 40% vodný roztok | 2 555a |
| Dusičnan sodný, 45% vodný roztok | 4 133 |
| Inertní látka | |
| Voda: celulosa | — b |
| a Střední hodnota z mezilaboratorních porovnávacích zkoušek | |
| b Maximální tlak 2 070 kPa nebyl dosažen | |
| c Nasycený roztok se připraví při 20 °C | |
IX.5 INTERPRETATION OF RESULTS
The results of the tests shall be evaluated taking into account:
(a) whether a mixture of test substance and cellulose has been spontaneously ignited; and
(b) to compare the average time of pressure rise from 690 kPa to 2,070 kPa with the time reported by the reference substance (s).
The liquid shall be considered an oxidant if:
(a) the mixture of the substance and cellulose is spontaneously ignited in a 1: 1 (m) ratio; or
(b) the average rise in pressure of the mixture of substance and cellulose in a ratio of 1: 1 (m) is less than or equal to the average increase in pressure of the mixture of 65% (m) of aqueous nitric acid and cellulose.
In interpreting the results, the test results of a substance with inert material shall also be taken into account to avoid incorrect results.
Figure 5
Figure 6
Figure 7
This decree shall take effect on the day of its publication.
Minister:
Mgr. Bublan v. r.
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Regulation Information
| Citation | Decree No. 10 / 2006 Coll., amending Decree No. 164 / 2004 Coll., laying down the essential methods for testing the hazardous properties of chemicals and chemical preparations in terms of flammable and oxidative properties |
|---|---|
| Regulation Type | - |
| Author | - |
| Collection | Code of Laws |
| Date of Promulgation | 12.01.2006 |
|---|---|
| Effective from | 12.01.2006 |
| Effective until | - |
| Status | Valid |
The regulation text is for informational purposes only.
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