Permeation in plastics packagings with the risk of creating explosive atmospheres … ·...

III.1 Dr. Goedecke – 04/2006, Seite 1/44

Permeation in plastics packagings with the risk of creating explosive atmospheres in

freight containers

December 3, 2007 / Geneva, Switzerland

Dr. Thomas Goedecke, Dr. John BethkeFederal Institute for Materials Research and Testing (BAM)

Berlin, Germany

ECOSOC Committee of Experts on the TDG and on the GHS


Introduction

Agenda

Calculation of Gas Concentration

Temperature Measurements

Air Exchange Measurements

Permeation Measurements

Results in a Real Container

Summary


Introduction

World container turnover

Container traffic in the world-wide most important container ports

Source: http://www.hafen-hamburg.de/content/view/33/33/lang,en/


IntroductionUN RECOMMENDATIONS ON THE TRANSPORT

OF DANGEROUS GOODSSpecific requirements for rigid plastics IBCs

6.5.5.3.2 The body shall be manufactured from suitableplastics material of known specifications and

be of adequate strength in relation to its capacity and its

intended use. The material shall be adequatelyresistant to ageing and to degradation caused by the

substance contained or, where relevant, by ultravioletradiation. Low temperature performance shall be taken into

account when appropriate. Any permeation ofthe substance contained shall not constitute a dangerunder normal conditions of transport.



OF DANGEROUS GOODSSpecific requirements for composite IBCs with

plastics inner receptacles

6.5.5.4.6 The inner receptacle shall be manufactured from

suitable plastics material of known

specifications and be of adequate strength in relation to itscapacity and its intended use. The material shall

be adequately resistant to ageing and to degradationcaused by the substance contained or, where relevant, by

ultraviolet radiation. Low temperature performance shall be

taken into account when appropriate. Anypermeation of the substance contained shall not constitute a danger under normal conditions of transport.



OF DANGEROUS GOODSSpecific requirements for plastics large packagings

6.6.4.3.1 The large packaging shall be manufactured fromsuitable plastics material of known

specifications and be of adequate strength in relation to itscapacity and its intended use. The material shall

be adequately resistant to ageing and to degradation caused by

the substance contained or, where relevant, by ultravioletradiation. Low temperature performance shall be taken into

account when appropriate. Any permeation of the substancecontained shall not constitute a danger under normal conditions of transport.


IntroductionRID / ADR 2007 for plastics drums and jerricans /

composite packagings (plastics material)

6.1.4.8.1Any permeation of the substance contained in the package, or recycled plastics material used to produce new

packaging, shall not constitute a danger under normal conditions of carriage.

6.1.4.8.7

The maximum permissible permeability for flammable liquids shall be 0.008 g/l*h at 23 °C (see 6.1.5.7).


IntroductionRID / ADR 2007 for plastics drums and jerricans /

composite packagings (plastics material)

6.1.5.7..Supplementary permeability test for plastics drums and

jerricans ….and for composite packagings (plastics material) ….intended for the carriage of liquids having a flash-point ≤ 60 °C …

Polyethylene packagings need be subjected to this test only if they are to be approved for the carriage of benzene, toluene, xylene or mixtures and preparations containing those substances.To be demonstrated by weighing before and after storage

for 28 days at 23 °C and 50% relative atmospheric humidity.

Criterion for passing the test: permeability shall

not exceed 0.008 g/l*h.


IntroductionRID / ADR 2007

rigid plastics IBCs / composite IBCs with plasticsinner receptacles / plastics large packagings

6.5.5.3.2 / 6.5.5.4.6 / 6.6.4.3.1

Any permeation of the substance contained shall not constitute a danger under normal conditions of carriage.


IntroductionRegulations

CFR49 part173 appendix B

Test Method 1:180 days at a temperature no lower than 18° C. (64° F.)

Test Method 2:28 days at a temperature no lower than 50° C. (122° F.)

Test Method 3:

14 days at a temperature no lower than 60° C. (140° F.)

Three sample containers shall be tested for each combination of hazardous material and size and design.

For poisonous substances, the rate of permeation

is limited to < 0.5% over the test period. For all other hazardous materials, the permeation rate

Is limited to < 2.0%.


Introduction

Factors influencing permeation:

Temperature

Solvent

Material

air exchangePermeation

% Lower Explosive Limit (LEL)

Permeation

Air Exchange Air Exchange

Freight Container

PlasticPackaging

PlasticPackaging

PlasticPackaging

PlasticPackaging


Introduction






Summary


General Purpose

Container 22G1

Refrigerated Container 22R1 Truck


BAM-Container 22G1 Ventilation Devices



Execution of the measurement

• inserting the indicator gas at the particular time t = 0

(SF6: sulfur hexafluoride )

• homogenization by a ventilator

• sampling in syringes at equal time intervals

• calculating the air-exchange-constant n:

ci: concentration at a particular time titi: particular time

�DIN EN ISO 12569

Thermal performance of buildings - Determination of air

change in buildings - Tracer gas dilution method

2

1ln1

12 tt

tt

c

c

ttn

=

=⋅

−=


Air exchange rate measurements during different loadings20´ container 22G1 with 32 ventilation devices


16 18 20 22 24 26 28 30 32

0.15

0.14

0.13

0.12

0.11

0.10

0.09

0.08

0.07

0.06

0.05

Loaded with 0 IBC

Loaded with 8 IBCAir

Exch

an

ge

Ra

te

(h-1)

Free Container Volume (m³)

Loaded with 16 IBC

0.04


0,001

0,01

0,1

1

10

100

22G1

outdoor

new (2)

22G1

indoor old

(2)

22G1

ventilated

indoor old

(32)

22G0

indoor old

22R1

indoor old

22G0 truck

new

22G1 truck

new (10)

Truck

indoor

Driving

truck

22G1

ventilated

empty (32)

22G1

ventilated

with 8 IBCs

(32)

22G1

ventilated

with 16

IBCs (32)

Container- / Truck-type (number in brackets after the type is the number of ventilation

devices)

air

ex

ch

an

ge

ra

te [

h-1

]

Air exchange rates of different containers and trucks

Comparison of

different loadings



Introduction






Summary



On lower deck container vessel „HongKongExpress“

-10

0

10

20

30

Sep

Okt

Nov

Dez

Tem

pera

ture

[°C

]

Time

30

40

50

60

70

80

90

100re

l. Hum

idity

[%]

Temperature

Dew Point

rel. Humidity

22.08.2003

20:00:00

13.12.2003

14:18:47

Tem

pe

ratu

re[°

C]

Re

l. H

um

idity

[°C

]

Temperature

Dew Point

Rel. Humidity

Sept. Oct. Nov. Dec.

Temperature

Dew Point

Rel. Humidity

Temperature

Dew Point

Rel. Humidity

Temperature

Dew Point

Rel. Humidity

TemperatureDew PointRel. Humidity


Transport Nanjing (China) to Giengen (Germany)

28.07.2005 to 27.09.2005

57.6 °°°°C

3.5 °°°°C

Temperature

100 %21 %Rel. humidity

Max.Min.

Source: Bosch und Siemens Hausgeräte GmbH

28.07.2005 11.08.2005 25.08.2005 08.09.2005 22.09.20050,0

6,0

12,0

18,0

24,0

30,0

36,0

42,0

48,0

54,0

60,0

0,0

10,0

20,0

30,0

40,0

50,0

60,0

70,0

80,0

90,0

100,0

relative Luftfeuchte

Temperatur

rela

tive L

uftfe

uchte

in %

Tem

pera

tur in

°C

Datum

Rel. humidityTemperature



Transport from Japan to Memphis (USA)

Source: DIMENSIONS.06, San Antonio, TEXAS April 18-21, 2006



Measuring equipment, load and power supply

2 IBCs 1000 lwith 2 thermocouples

4 drums 220 lwith 2 thermocouples

GPS- data logger

Temperature loggerShock-recorder

2 gel batteries 210 Ah



Transport and 3 week storage in Singapore

07.06.2006 21.06.2006 05.07.2006 19.07.2006 02.08.2006 16.08.2006

0

5

10

15

20

25

30

35

40

45

50

Truck and

train

Hamburg-Singapore

lower deck

container vessel

Singapore-Hamburg

on deck

container vessel

Singapore Habour

Air

Drum

IBC

Te

mpe

ratu

re

[°C

]

Date



Transport and 3 week storage in Singapore

00:00 06:00 12:00 18:00 24:00

0

5

10

15

20

25

30

35

40

45

50

Air Drum (vapour space) Drum (liquid)

IBC (vapour space) IBC (liquid)

Tem

pera

ture

[°C

]

Time

Singapore 2006/07/18



01.01.2007 01.02.2007 01.03.2007 01.04.2007 01.05.2007 01.06.2007

0

5

10

15

20

25

30

35

40

45

50

7654321

Air (top)

Drum (top)

IBC (top)T

em

pe

ratu

re [

°C]

Date

1 Berlin-Hamburg 2 Hamburg-Singapore (on deck)

3 Singapore Habor 4 Singapore-Melbourne5 Melbourne Habor 6 Melbourne-Hamburg7 Hamburg-Berlin



00:00 06:00 12:00 18:00 24:00

0

5

10

15

20

25

30

35

40

45

50

Air Drum (vapour space)

Drum (liquid) IBC (vapour space) IBC (liquid)

Tem

pera

ture

[°C

]

Time

Between Singapore and Malaysia 2007/02/13


Introduction






Summary


Permeation Measurementsat 23°C, 40°C and 50°C

drum

jerrican

IBC

Subject of application

Lupolen 5261 Z

Lupolen 5021 DX

Lupolen 4261 AGUV

Material

0.954

0.950

0.945

Density g/cm³

Solvents:trichloroethylene(representative for chlorinated hydrocarbons)

toluene(representative for aromatic compounds)

n-hexane

(representative for aliphatic compounds)



Lupolen 4261 AGUV, 23°C

1 2 3 4 50

1

2

3

4

5 trichloroethylene

toluene

n-hexane

Pe

rme

atio

n c

oe

ffic

ien

t P

[

]

Wall thickness d [mm]

g ⋅ m

m

m²⋅

h



3 mm, Lupolen 4261 AGUV

P0 = constant (= extrapolated permeation coefficient for T →→→→ ∞∞∞∞) EP = activation energy of permeationR = gas constantT = absolute temperature

TR

EPTP

⋅−= P

0ln)(ln

3,0 3,1 3,2 3,3 3,40

0,1

1

10

23 °C40 °C trichloroethylene

toluene

n-hexane

Ra

te o

f p

erm

ea

tio

n

Q [

]

1000/T [1/K]

g

m²⋅

h

50 °C


Effective protection against permeation

Permeation barriers:

- safety-layer

e.g. permeation barrier EVOH, PA

- fluorination

- nanoparticles


Permeation Measurements 0.4 l bottles, fluorinated surface with SMP, wall thickness

2.5 mm, 23°C, 41°C, 50°C; toluene

0 100 200 300 400 500 600 700 800 9000,00

0,05

0,10

0,15

0,20

0,25

0,30 temperature 41 °C and 50 °C

temperature 23 °C

Ra

te o

f p

erm

ea

tio

n

Q [

]

Time t [ h ]

g

m²⋅

h

temperature change


Permeation Measurements Lupolen 4261 AGUV / permeation barrier EVOH, 40°C, wall

thickness 2 mm

0 50 100 150 200 250 300 3500,0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8 trichloroethylene

toluene

n-hexane

Pe

rme

atio

n c

oe

ffic

ien

t P

[

]

Time t [ h ]

g ⋅ m

m

m²⋅

h


Introduction






Summary


Calculation of the Solvent Concentration

( )( )tn

IBCC

IBC exVVn

QAx ⋅−−⋅⋅−⋅

⋅⋅= 1β

= mass per unit volume in g / m3

x = number of IBCs

AIBC = surface of the IBC in m2

Q = rate of permeation in g / (m2h)

n = air change rate in h-1

VC = volume of the container in m3

VIBC = volume of the IBC

t = test duration in h

β


Calculation of the Solvent Concentration

ADR/RID 2007: Plastics drums and jerricans

6.1.4.8.7The maximum permissible permeability for

flammable liquids shall be 0.008 g/l * h at 23 °C.


Calculation of the Solvent Concentration16 IBCs filled with toluene, 20‘ freight container / 32 vents,rate of permeation 0.008 g/l*h, 23°C, air exchange rate 0.14 / h

0

5

10

15

20

25

30

35

40

45

0 1 2 3 4 4 5 6 7 8 9

Storage time [h]

Co

nc

en

tra

tio

n [

g/m

³]

LEL

concentration


Calculation of the Solvent ConcentrationRegulations

CFR49 part 173 appendix B

Test Method 1:180 days at a temperature no lower than 18°C. (64°F.)

Test Method 2:28 days at a temperature no lower than 50°C. (122°F.)Test Method 3:14 days at a temperature no lower than 60°C. (140°F.)

Three sample containers shall be tested for each combina-tion of hazardous material and size and design.

For poisonous substances, the rate of permeation is limited

to < 0.5% over the test period. For all other hazardous materials, the permeation rate is

limited to < 2.0%.


Calculation of the Solvent Concentration16 IBCs filled with toluene, 20‘ freight container / 32 vents,limit (CFR49/meth.2), 28 days at 50°C, air change rate 0.14 / h

0

5

10

15

20

25

30

35

40

45

0,0 0,2 0,3 0,5 0,7 0,9 1,0 1,2 1,4 1,6 1,7

Storage time [h]

Co

ncen

trati

on

[g

/m³]

LEL

concentration


Calculation of the Solvent Concentration16 IBCs filled with toluene, 20‘ freight container / 32 vents,limit (CFR49/meth.3),14 days at 60°C, air exchange rate 0.14 / h

0

5

10

15

20

25

30

35

40

45

0,00 0,16 0,33 0,49 0,66 0,82

Storage time [h]

Co

ncen

trati

on

[g

/m³]

LEL

concentration


Calculation of the Solvent Concentration16 IBCs filled with toluene, 20‘ freight container / 32 vents,rate of permeation 0.96 g/(m²*h), 40°C, air exchange rate 0.14 / h

0

5

10

15

20

25

30

35

40

45

0,0 2,5

5,0 7,5

10,0

12,5

15,0

17,5

20,0

22,5

25,0

Storage time [h]

Co

nc

en

tra

tio

n [

g/m

³]

LEL

concentration


Calculation of the Solvent Concentration16 IBCs filled with toluene, 20‘freight container / 0 vents, rate of permeation 0.03 g/(m²*h), 40°C, EVOH, air exchange rate 0.01 / h

0

5

10

15

20

25

30

35

40

45

0,0

10,0

20,0

30,0

40,0

50,0

60,0

70,0

80,0

90,0

100,

0

Storage time [h]

Co

ncen

trati

on

[g

/m³]

LEL

concentration


Calculation of the Solvent Concentration16 IBCs filled with toluene, 20‘ freight container / 0 vents, rate of permeation 0.05 g/(m²*h), 41°C, SMP, air exchange rate 0.01 / h

0

5

10

15

20

25

30

35

40

45

0,0

10,0

20,0

30,0

40,0

50,0

60,0

70,0

80,0

90,0

100,

0

Storage time [h]

Co

ncen

trati

on

[g

/m³]

LEL

concentration


Introduction






Summary


1

2

3

4

5

6

7

8

9

Set-up for concentration measurements in the test box; solvent: toluene


Gas Concentration MeasurementsExperimental set-up



Gas Concentration MeasurementsToluene concentration in the 1 m³ test box

0 100 200 300 400 500 600 700 800 900 10000

20

40

60

80

100

tests 1,3,4,6; 40°C

top

middle

bottom

test 5; 23°C

Co

nce

ntr

atio

n [%

LE

L]

Time [h]


Arrangement of the IR-sensors within the container

5 and temp.

4

2

1

3

6

7

9

8

temperature sensor at 5

Results in Real Container

Gas Concentration MeasurementsExperime ntal set-up


Toluene concentration in the heated container with 2 IBCs

Results in Real Container

Gas Concentration Measurements

0 2 4 6 8 10 12 14 16 18 20 220

5

10

15

20

25

top

middle

bottom

Co

nce

ntr

atio

n [

%L

EL

]

Time [d]


Introduction






Summary


Summary:

Temperature has the greatest influence on permeation.

Permeation barriers reduce the rate of permeation by

more than one decimal power.

Without protection against permeation the lower explosive limit (LEL) of toluene can be reached at 40 °C within a few

hours or days.

Air temperatures of approximately 50 °C in the container

and 40 °C in the packagings are normal conditions of carriage.


Summary:

Recommendations

Adding special provisions concerning documentation and identification of transport units with an explosion hazard caused by permeation in order to apply ventilation measures to remove any potentially explosive atmosphere prior to unloading the transport unit.

Adding an analogous permeation requirement in Chapter 6.1 (plastics drums, plastics jerricans, specific composite packagings (plastics material) and combination packagings with plastics inner packagings) as set out in 6.5.5.3.2, 6.5.5.4.6 and 6.6.4.3.1.

Adding provisions that the permeation requirements can be covered, if appropriate means are applied to all concerned packagings and IBCsto reduce the rate of permeation, or the packagings and IBCs are transported in containers with forced ventilation.

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