PDCR-12471中英翻译

1 Scope 范围

This document presents a screening procedure, based primarily on the use of

dimethylglyoxime, for the detection of nickel release from items that come into

direct and prolonged contact with the skin.

本文献提供了主要利用丁二酮肟快速测试直接及长期接触皮肤的样品的镍释放测试

方法。

2 Reference 参考文献

PD CR

12471:2002

3 Reagents 试剂

All reagents shall be of pro analysi grade or better.

所有试剂为分析纯或分析纯以上级别。

3.1 Deionized water

去离子水

3.2 Ammonia solution, about 10 % (m/m) NH

3

氨水，~10 % (m/m) NH

3

NOTE - This solution may be prepared from a more concentrated ammonia solution;

for example, one containing 24 % or 30 %(m/m) NH3.

这种溶液可由浓氨水稀释得到；如由24%或30%浓氨水稀释而得。

3.3 Sodium chloride, NaCI

氯化钠，NaCI

3.4 Lactic acid, CH

3

CHOHCOOH, ρ = 1,21 g/ml, > 88 %

乳酸，CH

3

CHOHCOOH， ρ = 1.21 g/ml, > 88 %

3.5 Urea, CO(NH

2

)

2

尿素，CO(NH

2

)

2

3.6 Dimethylglyoxime, C

4

H8N

2

O

2

, 99 %, or test strips for the detection of nickel,

containing dimethylglyoxime or other colorimetric reagent(s) with

approximately equivalent selectivity and sensitivity to nickel.

丁二酮肟，C

4

H

8

N

2

O

2

，99 %, 或含有用来检测Ni的丁二酮肟的试纸或其它的

具有与Ni 测试等同选择性和灵敏度的显色试剂。

3.7 Ethanol, C

2

H

5

OH, > 95 %

乙醇，C

2

H

5

OH, > 95 %

3.8 Hydrogen peroxide, H

2

0

2

, approximately 30 % (m/V) solution (100 volume).

(Not required for the pre-test, 5.3.4 or the field test, 5.3.6)

过氧化氢，H

2

0

2

，~30%（m/V）溶液（100体积）。（不用于前期处理5.3.4

及现场测试5.3.6）

3.9 Dithiooxamide (rubeanic acid), C

2

H

4

N

2

S

2

. (Not required for the pre-test or the

field test)

二硫代草酰胺（红氨酸), C

2

H

4

N

2

S

2

. 不用于前期处理及现场测试。

3.10 Sodium acetate trihydrate, C

2

H

3

NaO

2

3H

2

O. (Not required for the pre-test or

the field test)

三水乙酸钠，C

2

H

3

NaO

2

3H

2

O，（不用于前期处理及现场测试）。

3.11 Acetic acid, glacial, C

2

H

4

O

2

. (Not required for the pre-test or the field test)

冰醋酸，

C

2

H

4

O

2

，（不用于前期处理及现场测试）。

4 Equipment 设备

4.1 Flat-bottomed dish, made of glass or other non-metallic material. (Not

required for the pre-test)

平底碟子，由玻璃或其他非金属材料做成（不用于前期处理及现场测试）。

4.2 Thermometer, (0°C - 100°C) ± 1°C

温度计，(0°C - 100°C) ± 1°C

4.3 Pasteur pipette or, for the field test, a drop-dispensing bottle capable of

dispensing drops with an approximate volume of 50 µI.

用于现场测试的移液枪或能够滴取每滴约50 µI的滴瓶。

4.4 Cotton-wool-tipped sticks (white)

棉棒（白色）

4.5 pH meter or narrow-range pH paper

pH计或窄范围的pH试纸

4.6 Laboratory oven, capable of maintaining a temperature of 50°C ± 3°C

(required for the laboratory test, 5.3.5)

实验室用烘箱，能够保持 50°C ± 3°C（用于实验室测试5.3.5）

4.7 Heating/drying apparatus (required only for the field test)

加热/干燥设备（仅用于现场测试）

4.7.1 Hand-held hair dryer, or 手握式头发吹风机，或

4.7.2 Apparatus consisting of a light bulb, reflector type, (IEC 887: R80; 60 W to

100 W) mounted vertically downwards in a lamp holder positioned above a

flat base, such that the distance of the face of the bulb above the flat base

may be varied between approximately 40 mm and 120 mm.

含有电灯泡，反射类型，（IEC 887: R80; 60 W to 100 W）能够垂直照射于

一个平面正上方的设备。平面距离灯泡的距离可在约40 mm 至 120 mm之

间变化。

5 Procedure 过程

5.1 Preparation of solutions

溶液配制

Unless otherwise specified, the following solutions are stable for 6 months at

temperatures below 25°C.

除非有特殊指明，否则以下溶液在低于25°C时可保存6个月。

5.1.1 Dimethylglyoxime, 0,8% (m/V) alcoholic solution.

丁二酮肟，0.8% (m/V)乙醇溶液。

Weigh 0,8 g ± 0,05 g of dimethylglyoxime (3.6), dissolve and make up

to 100 ml in ethanol (3.7).

称取0.8 g ± 0.05 g dimethylglyoxime (3.6)，溶解并用乙醇（3.7）定容

至100 mL

5.1.2 Artificial sweat. 人工汗液

Transfer 1g ± 0,02 g urea (3.5), 5 g ± 0,1 g sodium chloride (3.3) and

1,13 g ± 0,02 g (940µl ± 20 µl) lactic acid (3.4) into a 2-litre beaker. Add

1000 ml deionized water (3.1) and stir. Using a pH meter or pH paper

(4.5), adjust the pH to 6,5 ± 0,2 by the dropwise addition of ammonia

solution (3.2) with stirring. Artificial sweat is stable for 6 months when

kept in the dark below 8°C in a closed container.

移取1g ± 0.02 g 尿素（3.5），5 g ± 0,1 g 氯化钠(3.3) 及 1.13 g ± 0.02

g (940µl ± 20 µl) 乳酸 (3.4)至2 L 烧杯中。加1000 ml 去离子水 (3.1)

并搅拌. 逐滴加入氨水溶液(3.2)并不断搅拌用pH计或pH试纸(4.5), 调整

pH至 6.5 ± 0.2 。在8°C 下黑暗密封条件下可保存6个月。

NOTE - The use of a pH meter is preferable to the use of narrow-range pH paper.

与窄范围pH试纸相比pH计是较好的选择。

5.1.3 Dithiooxamide, 0,5% (m/V) alcoholic solution.

二硫代草酰胺, 0,5% (m/V)乙醇溶液

Weigh 0,5 g ± 0,05 g of dithiooxamide (3.9), dissolve and make up to

100 ml in ethanol (3.7).

称取0,5 g ± 0,05 g 二硫代草酰胺 (3.9)，用乙醇（3.7）溶解并定容至

100mL。

5.1.4 Sodium acetate buffer solution, pH 4.5.

醋酸钠缓冲溶液，pH4.5.

Weigh 5,6 g sodium acetate trihydrate (3.10) and add 2,4 ml glacial

acetic acid (3.11). Dissolve and make up to 10 ml with water.

称取5.6 g 三水合醋酸钠，并加入2.4mL冰醋酸（3.11）。用水溶解并定

容至10mL。

5.2 Sample preparation

样品制备

5.2.1 The surfaces to be tested are those that come into direct and prolonged

contact with the skin. The surface(s) of the item to be tested shall be

cleaned with ethanol (3.7) using a cotton-wool-tipped stick (4.4).

测试样品为直接或长期与皮肤接触的表面。测试面应该用蘸有乙醇（3.7）

的棉棒（4.4）清洁。

NOTE 1 - This cleaning stage is intended to remove extraneous grease and skin

secretions due to handling, but not any protective coatings. However, it will

also substantially remove any nickel salts present on the surface of the test

item. If there is a requirement to detect the presence of surface

contamination by nickel, this cleaning stage should be omitted.

这个阶段的清洁是为了脱去样品外部的油脂以及由于触摸沾有的皮肤分泌物，

而不是保护层。然而，这也会脱去测试面存在的一些镍盐。如果有测试样品表

面的镍的情况，这个阶段的清洁工作应该取消。

NOTE 2 - An item may be composed of parts made of different materials, each of which

may require testing if they come into direct and prolonged contact with the

skin.

样品可能有不同材料组成，每个与皮肤直接或长期接触的部件都应该进行测试。

NOTE 3 - Contamination by objects containing nickel (paper-clips, rivets, coins, etc.)

may give false positive results if such objects come into contact with test

items, surfaces, reagents or the hands. This possibility should be eliminated

by avoidance of nickel-containing objects, washing the hands before

performing the tests and performing blank tests.

如果样品，测试表面，试剂或手与含有Ni的物质（纸夹，铆钉，钱币等等）接

触而污染会导致出现阳性结果。这种可能性可通过避免与这些污染物质接触及

测试前清洗手并制备空白而消除。

5.2.2 The presence of coatings, such as paint, lacquer and electroplate, can

prevent the detection of a nickel-releasing substrate. Therefore, abrasion

of the surface prior to testing for nickel-release should be considered,

especially if a negative result (see 6.2) has been obtained on the

unabraded item. This may be achieved using emery paper, emery board

or other nickel-free abrasive material.

涂层的存在，如漆，清漆以及电镀，能阻止样品基材Ni的检测。所以应该

考虑到在测试前对样品表面进行打磨，尤其是对于没有进行打磨的样品测

出阴性结果(参考 6.2)的情况。可以使用金刚砂，金刚砂板或其它Ni释放

打磨材料进行打磨。

CAUTION This procedure is likely to damage the item.

这个过程可能会损坏样品。

NOTE - If a positive result is obtained in these circumstances, testing in accordance

with EN 12472 is required to check compliance with EU Directive 94/27/EC.

这三种情况下如果得到阳性结果，需要依据EN 12472进行测试以确认其是否符

合EU Directive 94/27/EC。

5.3 Test methods

测试方法

5.3.1 The person carrying out the tests shall have a normal colour vision in

regard to being able to detect red and pink colours.

进行测试人员应具有正常的识别红色及粉红色的能力。

5.3.2 Check the reactivity of the test solutions, as necessary, by applying the

test to a known nickel-releasing surface, e.g. a cupro-nickel coin.

检查测试溶液的活性，如果需要，可通过测试已知Ni释放样品的表面进行

验证。如：铜镍合金片。

5.3.3 Either conduct the pre-test (5.3.4) and/or the laboratory test (5.3.5) or

the field test (5.3.6).

或进行预处理(5.3.4)或实验室测试(5.3.5)或现场测试(5.3.6)

a) If the pre-test is conducted and a positive result (red colouration) is

observed, further testing is unnecessary unless the presence of iron is

suspected (see 5.3.8);

若预处理测试得到红色阳性结果，则不需要进一步的测试，除非可能存在铁

离子。

b) If the pre-test is conducted and a negative result (absence of red

colouration) is observed, conduct the laboratory test (5.3.5) or the field test

(5.3.6).

若预处理测试得到无红色阴性结果，进行实验室测试(5.3.5)或现场测试(5.3.6)

NOTE - The pre-test only gives a positive result in the presence of nickel salts or

where nickel is available for release from an item without prior corrosion (see

clause 2).

预处理测试仅在存在镍盐或样品在没有预先侵蚀的情况下释放出镍时显示阳

性结果。

5.3.4 Pre-test for nickel release: moisten a cotton-wool-tipped stick (4.4) with

one or two drops of dimethylglyoxime solution (5.1.1) and one drop of

ammonia solution (3.2). Check that there is no discolouration. Rub firmly

the cotton wool tip for 15 s against the surface to be tested. View the stick

against a white background. The appearance of a red colour, from light

pink to strong cerise, indicates nickel release.

预处理镍测试：用带有1-2滴丁二酮肟(5.1.1)溶液及1滴氨水溶液(3.2)的棉

棒，检查是否变色，轻轻擦拭样品测试表面15s。在白色背景下观察。观察

红色的出现，从浅红至深樱桃色表明有镍释放。

5.3.5 Laboratory test: place the test item on a dish (4.1) and pre-heat it to

approximately 50°C. Using a Pasteur pipette, transfer one drop of artificial

sweat (5.1.2) onto the surface to be tested. Dry the item in the laboratory

oven (4.6) until its surface is completely dry. The temperature shall be

50°C ± 3°C. Drying time will be about 15 min. Perform the test for nickel

release (5.3.7, 5.3.8 or 5.3.9, as appropriate).

实验室测试：将测试样品放置碟子上(4.1) 并热至50℃。用移液枪将1滴人

工汗液(5.1.2) 滴至样品表面。在50±3℃的烘箱 (4.6) 中干燥直至样品表面

完干燥，干燥大约15min。进行镍释放测试(5.3.7, 5.3.8 or 5.3.9, 适当选择)。

5.3.6 Field test: place the test item on a dish (4.1) and using a Pasteur pipette

or a drop-dispensing bottle (4.3) put one drop of artificial sweat (5.1.2) on

the surface to be tested. Dry the surface completely with the hair dryer

(4.7.1). If necessary, keep the item in place using any suitable means.

Place a thermometer (4.2) close to the test item. The temperature shall not

exceed 50°C.

现场测试：

样品放置碟子（4.1）上，用移液枪或滴瓶（4.3）将1滴人工汗液

（5.1.2）滴至样品表面，用吹风机（4.7.1）将样品表面吹干，如果需要可用其

他加热设备（4.2）将样品表面干燥，但温度不超过50℃

Alternatively, the test item can be dried by the heat from an electric light

bulb usi。ng the equipment described in 4.7.2. The light bulb is switched on

and allowed to warm up. Raise or Iower the lamp holder to obtain a

constant temperature of approximately 50°C just above the surface on the

flat base directly beneath the lamp. Place the test item on a dish directly

beneath the centre of the lamp. Pre-heat the item for about 10 min then put

one drop of artificial sweat on the surface to be tested. Allow the surface to

dry completely.

另外，可以用灯泡预热样品，如4.7.2所描述设备。打开灯泡以加热。将样品

置于灯泡正上方，通过上下距离调节温度在大约50°C，预热10min，然后将

1滴人工汗液滴至样品表面进行测试，表面完全干燥后进行测试

Perform the test for nickel release (5.3.7).

进行镍释放测试(5.3.7)。

5.3.7 Testing for nickel release: allow the item to cool for approximately 5 min.

Moisten a cotton-wool-tipped stick (4.4) with one or two drops of

dimethylglyoxime solution (5.1.1) and one drop of ammonia solution (3.2).

Check that there is no discolouration. Place the tip of the

cotton-wool-tipped stick onto the area to be tested and rub gently for 5 s.

View the stick against a white background. The appearance of a red colour,

from light pink to strong cerise, indicates nickel release.

镍释放测试：冷却约5min，1至2滴丁二酮肟(5.1.1)及1滴氨水(3.2)润湿棉

棒(4.4)并检查是否变色，在样品表面用棉棒轻轻摩擦5s，在白色背景下观察

颜色的变化，若出现红色，从粉红色到深樱桃色表明有Ni释放。

Using test strips for the detection of nickel: Allow the item to cool and

immediately put one drop of ammonia solution (3.2) on the dried salts.

Place the test strip (3.6) onto the treated area for 5 s. View the strip against

a white background. The appearance of a red colour, from light pink to

strong cerise, indicates nickel release.

用试纸测试：冷却后快速加1滴氨水(3.2)在已干的盐上，并将测试试纸(3.6)

在处理过的样品表面置5s，在白色背景下观察测试试纸颜色的变化，若出现

红色，从粉红色到深樱桃色表明有Ni释放。

Note - Due to the corrosion induced by the artificial sweat and formation of salts on the

surface, shorter time and pressure is needed for the testing in 5.3.7 than when

performing the pre-test (5.3.4).

由于人工汗液引起的侵蚀以及盐的形成，在5.3.7的测试中需要较短的时间以及压力

较预处理测试(5.3.4)。

5.3.8 Checking for interference by iron (laboratory test only):

铁离子干扰（仅对实验室测试）：

when stainless steel or other iron-containing items are tested, ferrous

ions can cause a red or reddish-brown colouration. This colouration can

interfere with the detection of nickel. In order to eliminate the influence of

iron, the test (5.3.7) should be modified in the following way. After

allowing the test item to cool for approximately 5 min, moisten the tip of a

cotton-wool-tipped stick (4.4) with one or two drops of dimethylglyoxime

solution (5.1.1) and one drop of ammonia solution (3.2). Place a drop of

hydrogen peroxide solution (3.8) onto the surface to be tested. This

oxidises ferrous ions (Fe ) to ferric ions (Fe ). Rub the test area gently

with the cotton wool tip for 5 s. View the stick against a white background.

The appearance of a reddish colour indicates nickel release. The

appearance of other colours can mask a pale pink colour and hence

conceal the presence of nickel.

当测试样品为不锈钢或其它含铁的样品时，二价铁离子能产生红色或暗红棕色

这种颜色能够引起镍检测的干扰。为了消除这种干扰，（5.3.7）可按如下方式

进行修改。样品冷却约5min，在棉棒上滴加1-2滴丁二酮肟

(5.1.1)

和1滴氨水

(3.2)。在样品测试表面滴加一滴过氧化氢(3.8)。这可以将二价铁离子氧化

为三价铁离子。用棉棒在样品表面轻擦5s。在白色背景下观察棉棒，若有

淡红色出现表明有镍释放。其它颜色的出现能够掩饰暗红色的出现，以致掩

饰了镍的存在。

WARNING 100 volume hydrogen peroxide solution is corrosive and can cause

burns. In contact with combustible material it can cause fire. If test

strips are used, oxidation may be achieved by leaving the strip in the

air for 15 min, rather than by the addition of hydrogen peroxide

solution to the surface to be tested.

100体积的H

2

O

2

溶液具有腐蚀性并且容易引起燃烧。若接触易燃物质

可能会引起火灾。如果使用测试试纸，可以将试纸置于空气中15min

完成氧化，而不是在测试样品表面加H

2

O

2

。

NOTE - Some test strips contain masking agents for iron. For more information read the

manufacturers' instructions.

某些测试试纸包含铁离子掩盖剂。更多的信息，阅读生产商说明。

5.3.9 Confirmation of nickel release:

镍释放的确认

if desired, the release of nickel from an item may be confirmed after

repeating the sample preparation (5.2) and the laboratory test (5.3.5). It

shall not be performed directly after 5.3.7, testing for nickel release.

如果需要，样品中的镍释放可按下进行确认。重新按前述方法制样，并进行

实验室测试（Laboratory test），不可在进行Ni释放测试5.3.7后直接重

新测试Ni释放

Allow the object to cool for approximately 5 min. Place the tip of a

cotton-wool-tipped stick moistened with one drop of acetate buffer (5.1.4)

and one or two drops of dithiooxamide solution (5.1.3) onto the surface to

be tested and rub gently for 5 s. View the stick against a white

background. The appearance of a black-violet colour indicates nickel

release.

冷却约5min，在棉棒上滴加1滴醋酸盐缓冲溶液(5.1.4)及1-2滴二硫代草酰胺

溶液(5.1.3)，在样品表面用棉棒轻轻磨擦5s，在白色背景下观察颜色的变化，

若出现紫黑色，则表明有Ni释放。

NOTE - This test is not intended as a substitute for testing with dimethylglyoxime (see

5.3.7), and it is recommended primarily for the confirmation of nickel release.

However, because of its ability to discriminate between nickel and iron release, it

may be performed in addition to 5.3.7 and/or 5.3.8 when testing items that contain

iron, e.g. stainless steels, and used to assist in the interpretation of results.

这个测试不是丁二酮肟的替代测试（参考5.3.7），它主要是用来作为镍释

放的确认。然而，由于其能分辨出镍释放和铁释放，所以在测试如不锈钢等

含铁样品时，可以附加于实验室测试5.3.7及/或5.3.8之后来帮助解释结果。

6 Interpretation of results 结果解释

6.1 Positive result 阳性结果

Formation of a red colour, from light pink to strong cerise, with

dimethylglyoxime indicates that the nickel release from a tested surface is

likely to be greater than 0,5 µg/cm /week, and a positive result should be

reported.

在丁二酮肟显色剂作用下形成的红色，从浅红到深樱桃红，表明样品表面的镍

释放可能超过0.5 µg/cm /week。可以报出阳性结果。

Formation of a black-violet colour with dithiooxamide confirms a positive

result obtained with dimethylglyoxime.

在二硫代草酰胺的作用下形成的黑紫罗兰色的出现确认了丁二酮肟得出的阳

性结果。

6.2 Negative result 阴性结果

No colour change in both or either of these tests, indicates an absence of

nickel release, and a negative result should be reported. However, such a

result should be interpreted cautiously since these tests are of short duration

and the test conditions are not comparable with those in EN 1811. The

apparent absence of nickel release should be confirmed by EN 1811 or EN

12472 (followed by EN 1811), as appropriate.

所有测试或其中之一，表明没有镍释放，可以报出阴性结果。然而，这样的结

果应谨慎报出，因为这些测试时间较短而且测试环境与EN 1811并不相符。适

当情况下，明确的没有镍释放的结果应该通过EN 1811 或EN 12472及 EN

1811确认。

6.3 Uncertain result 不确定结果

Apart from nickel, colouration in these tests can occur from metals such as

cobalt, copper and palladium and mask any red colouration from nickel.

Where colours other than red are obtained, the result should be reported as

uncertain. In such cases, it is advisable to apply the appropriate reference

method, EN 1811 or EN 12472 (followed by EN 1811).

除了镍离子，这些测试中金属中的Co，Cu以及Pd也能够产生颜色，这些颜色

能够掩盖镍的显色。当有非红色颜色出现时，结果应报出不确定结果。在这种

情况下，选择合适的参考方法EN 1811 或 EN 12472 及 EN 1811是比较明智

的。

7 Test report 测试报告

The test report shall include at least:

测试报告至少包含以下信息：

a) Identification of the sample including source, date of receipt, form of sample;

样品特定信息包括来源，接受日期，样品形态。

b) A reference to this document and to the test(s) performed;

测试样品测试参考文献

c) Nickel release described in accordance with clause 6 (i.e. positive, negative or

uncertain), specifying which part(s) of the item has(have) been tested;

一句条款6描述的镍释放（如阳性，阴性或不确定），指明测试样品哪部分已经

测试

d) Details of any deviations from the test procedures;

任何偏离测试程序的细节

e) Any unusual features observed during the testing;

测试过程中任何不正常的特征

f) Date of test;

测试日期

g) Signature of the operator.

操作日期