Life cycle of three BUONAPART‐‐E nanomaterialsand ...users.abo.fi/rzevenho/D6-4Annex2pres8 iuta Folien_Vortrag_Turku2_… · BG during Cu NP particle production OSU during Cu

FP7European Union Funding

for Research & Innovation

Life cycle of three BUONAPART‐ELife cycle of three BUONAPART‐E nanomaterials and corresponding products

U. Sager, B. Stahlmecke, T. A. J. Kuhlbusch, H. Kaminski, C. Asbach (IUTA); M. Stein, E. Hontañon, E. Kruis (UDE);

M. Stadlbauer (TKSE); L. Santos, F. Carrasco Torres (FOMENTEX);J. Gómez (AIT); I. Chang (MNL)

www.buonapart‐e.eu

Case studies: Nanoparticles and endproducts

Copper NP suspended in water

cooling agent

Silver NP introduced to textiles

medical clothes

Zinc NP in polypropylene

electric cable coating

www.buonapart‐e.eu FP7European Union Funding


General product life cycle of NP/NM and release paths



Schematic of material flow during life cycle



Cu NP in cooling agent – Process steps

• production of the Cu NP by an arc‐based process





b• bagging





b• bagging

• transport to subsequent processing

• preparation of the suspension in the laboratory





b• bagging



• filling of the cooling agent into the test circuit





b• bagging



• filling of the cooling agent into the test circuit

• end of the experiments

cleaning of

p

emptying of the test circuit

separation of the phases cleaning of the laboratory and the facilities

separation of the phases

re‐use or disposal



Sketch of the product life cycle of Cu NP in cooling agent

productionof Cu NP

end of useprocessing

use in acooling

WIof Cu NP

preparation of cooling

p gcircuit

arc-based bagging

WI

WWT

landfillp p

suspension agentbasedprocess

bagging

recyclingWWT

air ilf tair(workplace and ambient) soilsurface water

subjects of protectionenvironmenthumans



Production and material properties of Cu NP

• closed production facility, normally no exposure to air• leakage or exposure to air possible in case of failureleakage or exposure to air possible in case of failure danger of possible self‐ignition and explosion

a) b)

nominal size 65 nm,ignition > 130 °C

c) d)

ignition > 130 C,time b)‐c) 8 s,time c)‐d) 26 s



Measurement of release to air during production and bagging

• particle number concentration in office rooms ~ 10,000 #/cm³

• background particle number concentration in the test lab ~ 2,000 #/cm³

• during measurements: 13 units of the mOSU workingmaterial input: copper shots

• equipment: 2 FMPS, 1 SMPS, 1 CPC particle number concentration particle size distribution

• sampling (NAS) + SEM + EDX particle characteristics



Release of Cu NP during production phase with mOSU

1.0E+04Start generatorignition Cu NP production

Switch off individual

OSU

System off completely

even

t

8.0E+03

[#/c

m³]

13 OSU are running

During switch off: SMPS measurements of NP-particles produced

und

part

icle

e

6.0E+03

entr

atio

n

FMPS near field backgroundFMPS OSU systemSMPS OSU systemow

n ba

ckgr

ou

4.0E+03

ber c

once SMPS OSU system

Unk

no

2.0E+03Num

b

0.0E+0011:00 11:30 12:00 12:30 13:00 13:30 14:00 14:30 15:00 15:30 16:00 16:30

FMPS after electrometer zeroing



Particle size distributions in the mOSU, mOSU surroundingsand the near field background during production

1.0E+06BG during Cu NP particle productionOSU during Cu NP particle production

1.0E+05

³]

FMPS detection limitSMPS Cu NP produced with 13 OSU

1.0E+04

gdp [

#/cm

1.0E+03

dN/d

log

1.0E+02

1.0E+011 10 100 1,000

Particle diameter dp [nm]



p

Release of Cu NP during bagging

3.0E+04Pressure shock on filter after passivation

Bagging handling

Welding of the bag

2 0E+04

2.5E+04

[#/c

m³]

Start opening OSU system

System closed

1.5E+04

2.0E+04

entr

atio

n

1.0E+04

ber c

once

FMPS near field backgroundFMPS OSU systemSMPS OSU system

5.0E+03Num

b

0.0E+0010:30 10:40 10:50 11:00 11:10 11:20 11:30 11:40



Measurement of release to air during preparation of suspension

• tests with reduced cooling agent volume 40 ml

• sample was weighed in in the fume hood, i d ith DI t d di d b lt i d f 30 imixed with DI water and dispersed by ultrasonic sound for 30 min.

• 3 steps of preparation 3 vol %• 3 steps of preparation 3 vol.‐%

• equipment: 2 FMPS / CPC particle number concentrationequipment: 2 FMPS / CPC particle number concentration particle size distribution

• sampling (NAS) + SEM + EDX particle characteristics







NAS

CPC

FMPSFMPS



Release of Cu NP during the preparation of the suspension

4.5E+03

5.0E+03m

³] Cu NP weighing and

Cu NP weighing and

Cu NP weighing and Fe NP

Start measurement

setup

3.5E+03

4.0E+03

tion

[#/c

m weighing and ultrasonic

weighing and ultrasonic

weighing and ultrasonic ultrasonic. . . .

2.5E+03

3.0E+03

once

ntra

t

FMPS near field background

1.5E+03

2.0E+03

num

ber c

o FMPS laboratory hood

5 0E+02

1.0E+03

5 03

Part

icle

n

0.0E+00

5.0E+02

10:00 10:30 11:00 11:30 12:00 12:30 13:00 13:30 14:00

P



Material flow during the life cycle of Cu NP used in cooling agent (accidental release not considered)

raw material input

i t d C NP d ti100 %

air

soil

water

< 0.01 %

0 %

0 %

air

soil

water

< 0.01 %

0 %

0 %passivated Cu NP production

bagging

98 %

30 %

soil

WWTP

WIP

landfill

recycling

1 %

60 %

2 %7 %

0.1 %

1.6 %

0.1 %0.2 %

WWTP

WIP

landfill

recycling air< 0.01 %

preparation of suspension

filling of suspension

air

soil

watersoil

water

WWTP

WIP

0 %

0 %

1 %1 %

98 %

< 0.01 %

0 %

0 %0 %

use of cooling agent

filling of suspensioninto test circuit1 %

1 %WWTP

WIP

landfill

recycling

air

water

WWTP

landfill

recycling

0 %

0 %98 %0 %

0 %

0 %0 %

0 %

0 %

soil

end of use of cooling agent

0%0 % 20 % 0 % 0 % 0 %80 %

WIP

landfill

recycling

100 %0 %

0 %0 %

specific recyclingfor reuse

landfill WIP WWTP airwatersoil

WIP waste incineration plant WWTP Waste water treatment plantAssumptionMeasurement / impossible flow

0%0 % 20 % 0 % 0 % 0 %80 %

95 % 5 %



Resumé : Life cycle of Cu NP in cooling agent

• release during normal operation of production, bagging, preparation of suspension negligible or minor

• safety measures are necessary (e.g. self‐ignition)

• highest risk of release identified for disposal phase via waste water (high uncertainty)

• hazard potential of nanomaterial will change during life cycle d f idue to transformation processes



Ag NP in textiles/medical clothes – Process steps

• production of the Ag NP by an arc‐based process

• recovery of the Ag NP from the reactor Ag NP powder• recovery of the Ag NP from the reactor Ag NP powder


• preparation of the coating suspension

• coating of the textiles (different processes under evaluation)

• drying and/or fixation of the coating by heating

• further processing: sewing of medical clothescleaning of

the facilitiesfurther processing: sewing of medical clothes

• use of medical clothes including washing

h d f di l lid

the facilities

• at the end of use disposal as solid waste



Sketch of the product life cycle of Ag NP in medical clothes

productionuse of

medical end of use

WIof Ag NP

coating sewing wearinghi

arc-based

processing clothes

bagging annealing

WI

WWT

landfillg g

washingbasedprocess

bagg g g

recyclingWWT

air soilsurface water(workplace and ambient)

i t

soilsurface water

hsubjects of protection

environmenthumans



Planned tests on release

• further leaching tests during wet cleaning of the textiles /determination of Ag NP in the leaching agentdetermination of Ag NP in the leaching agent

• measurements at workplaces during the different steps ofmeasurements at workplaces during the different steps of processing

• abrasion tests with coated and uncoated textile samples



Material flow during the life cycle of Ag NP in medical clothes(accidental release not considered)

raw materialinput

A NP d ti

100 %air

water

2 %

0 %

0 %

soil

< 0.01 %*

* deduced from measurements of the Cu NP case study

Ag NP production

bagging

30 %

98 %

WWTP

WIP

landfill

recycling60 %1 %

7 %2 %

air

water0 %

0.1 %0.2 %

air

soil

water

WWTP

WIP

landfill

recycling

0 %

0 %

0.1 %1.6 %

< 0.01 %*

< 0.01 %*

preparation ofsuspension

coating

98 %

WWTP

WIP

landfill

recycling0 %

0 %1 %1 %

0 %soil

air0 %

0.1 %

recycling 1.6 %

18 %1 %

air

soil

water

WWTP

WIP

0.1 %

0 %

0 %

0 %

5 %

95 %

%

drying - annealing

sewing (i l tti )

water

WWTP

WIP

landfill

recycling0 %

0 %

0 %1 %

0 %

0 %

soil

0 %

landfill

recycling

0 %

80 %

0 %15 %

air

soil

water

WWTP

WIP

0.2 %

0 %

0 %

0 %

1 % 5 %

95 %

98.9 %

skin1 %

(incl. cutting)

wearing washingmedical clothes

82.8 %

d f

air

water

WWTP

WIP

landfill

recycling0 %

0 %0 %

20 %

0 %

0 %

0 %

soil

WIP

landfill

recycling

0 %

2 %

0 %0 %

air

soil

water

WWTP

WIP

landfill

recycling

0 %

1 %

0 %

0 %

0 %78 %

5 %

95 %

recycling landfill WIP WWTP airwatersoil

end of use 98 %2 % 0 % 0 % 0 % 0 %0 %


y g

> 99 % < 1 %



Resumé : Life cycle of Ag NP in medical clothes

• release during normal operation of production and bagging is expected to be negligible (analog to Cu NP case study)

• no risk of self‐ignition and explosion• general safety measures for handling with nanoobjects• main release in the use phase by abrasion during wearing and

washing effects of contact with the skin effects of Ag NP in waste water and WWTP

• end of use: medical clothes normally incinerated?• hazard potential of nanomaterial will change during life cycle

due to transformation processes• special concern due to high likeliness of exposure of humans



Zn NP in PP coating of cables – Process steps

• production of the Zn particles by an arc‐based process• recovery of the Zn NP from the reactor Zn NP powderrecovery of the Zn NP from the reactor Zn NP powder• transport to subsequent processing• separate supply of Zn NP powder and PP pellets to extruderseparate supply of Zn NP powder and PP pellets to extruder



Zn NP in PP coating of cables – Process steps

• production of the Zn particles by an arc‐based process• recovery of the Zn NP from the reactor Zn NP powderrecovery of the Zn NP from the reactor Zn NP powder• transport to subsequent processing• separate supply of Zn NP powder and PP pellets to extruderseparate supply of Zn NP powder and PP pellets to extruder• in the extruder: mixing of Zn NP and PP pellets by a screw,

heating, meltingheating, melting• exit of the extruder: cooling by injection into water• drying and forming of pelletsdrying and forming of pellets • further processing: coating of cables• use as a cable in buildings and other environments

cleaning of the facilities

use as a cable in buildings and other environments• at the end of use disposal as solid waste



Sketch of the product life cycle of Zn NP in cable coatings

productionuse ofelectric

end of useWI

of Zn NP

filling ofextruder

cablecoating

abrasionweathering

arc-based

processing cables

bagging extruding

WI

WWT

landfill

extruder coating weatheringprocessgg g g

recycling

WWT

air soilsurface water(workplace and ambient)

i t

soilsurface water

hsubjects of protection

environmenthumans



Planned tests on release

• measurements and analysis of released particles in the surroundings of the extruder g

• abrasion tests with the PP equipped with Zn NPabrasion tests with the PP equipped with Zn NP

• combustion tests with the PP equipped with Zn NP• combustion tests with the PP equipped with Zn NP



Material flow during the life cycle of Zn NP in cable coatings(accidental release not considered)

raw materialinput

Zn NP production

100 %

* deduced from measurements of the Cu NP case studyair

water

2 %

0 %

0 %

soil

< 0.01 %*

Zn NP production

bagging98 %

air

water0 %

0 %

0.1 %

WWTP

WIP

landfill

recycling60 %1 %

7 %2 %

0.1 %0.2 %

air

soil

water

WWTP

WIP

landfill

recycling

0 %

0 %

0.1 %1.6 %

< 0.01 %*

30 %

filling ofextruder

extruding

98.9 %

WWTP

WIP

landfill

recycling0 %

0 %1 %0 %

0 %soil

air

water0 %

0 %

1 %

soil

recycling 1.6 %

10 %1 %

air

soil

water

WWTP

WIP

1 %

0 %

0 %5 %

95 %

cable coating

electrical cables

94 %

WWTP

WIP

landfill

recycling0 %

0 %5 %0 %

air

soil

water

0 %

1 %

1 %

landfill

recycling

0 %0 %

88 %

air

water

0 %5 %

< 0.001 %

abrasion weatheringelectrical cables

end of use 85 %5 % 5 % 5 % 0 % 0 %0 %

1 %

1 %WWTP

WIP

landfill

recycling

0 %

0 %96 %

WWTP

WIP

landfill

recycling0 %

0 %0 %0 %

< 0.001 %soil95 %

recycling landfill WIP WWTP airwatersoil


> 99 % < 1 %

95 % 5 %



Resumé : Life cycle of Zn NP in cable coatings

• release during normal operation of production and bagging is g p p gg gexpected to be negligible (analog to Cu NP case study)

• safety measures are especially necessary due to pyrophoricity/ self‐ignition and low minimum ignition energyg g gy

• low release rates expected for use in cable coatings

• Zn recycling maybe coupled with Cu recycling of the cable



Summary and Outlook

• three cases analysed with respect to safety issues for their life cycle

• comparison shows high similarities for the production and processing phases and high similarities for the production and processing phases and high differences in use and end‐of‐life phases

• pyrophoricity identified as a major point of safety concern for the production of nanoscale metallic particles

• this life cycle analysis facilitates the safe‐by‐design approach and the identification of potential risksthe identification of potential risks



Acknowledgement

The work is part of the European Union’s SeventhF k d o 280765Framework program under grant agreement no 280765.http://www.buonapart‐e.eu



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