Presented to ISO/TC 194 / WG11 Chicago, Illinois July 13… and White... · Presented to ISO/TC 194 / WG11 Chicago, Illinois July 13, 2006. ... ASTM D6348 -98 ... ISO_TC 194 07_13_06

Ethylene Oxide Residuals

An Alternative Testing Method

Presented to ISO/TC 194 / WG11

Chicago, Illinois

July 13, 2006

Scientific AssumptionsScientific Assumptions

The rate limiting factor in The rate limiting factor in offgassingoffgassing is is the rate of release of the residue from the rate of release of the residue from the material, regardless of the matrix the material, regardless of the matrix being released intobeing released into

The rate of transfer of EO into clean air The rate of transfer of EO into clean air or nitrogen is equivalent to the rate of or nitrogen is equivalent to the rate of transfer into clean water based upon transfer into clean water based upon research by 3M scientistsresearch by 3M scientists

An Innovative New Alternative toAn Innovative New Alternative to

Existing Technologies ….Existing Technologies ….

• Detection of acids, bases, volatiles and semi-volatiles

simultaneously

• Quantitation and identification of compounds

• Fast collection and analysis time – Get Product to

Market Faster

• Low detection limits as required by guidelines

Historical Use of IR for EOHistorical Use of IR for EO

Proposed method is FTIR, not IRProposed method is FTIR, not IR

Interference problems were present in the Interference problems were present in the

past due to fixed wavelength IR past due to fixed wavelength IR technologytechnology

Subtraction of InterferenceSubtraction of Interference

0

1

2

3

4

4500 4000 3500 3000 2500 2000 1500 1000

Absorbance / Wavenumber (cm-1) Paged Z-Zoom CURSOR

File #21 = A0000728 6/13/2006 1:24 AM Res=None

Ultimum EV part 3, static,~10m,~37C,1.1935atm,0.5cm-1,64sc,MEC

-4

-2

0

2

4

4500 4000 3500 3000 2500 2000 1500 1000

Absorbance / Wavenumber (cm-1) Paged Z-Zoom CURSOR

File #24 : SUBTRACT Res=None

Effects on InterferenceEffects on Interference

0 100 200 300 400 500 600 700 800

Minutes

0.0

10.0

20.0

30.0

ppm

Ethylene_Oxide

0 100 200 300 400 500 600 700 800

Minutes

0.0

20.0

40.0

60.0

80.0

ppm

Ethylene_Oxide

FTIR Spectra of EO/ECH/EGFTIR Spectra of EO/ECH/EG

0

50E-05

.001

.0015

.002

.0025

4000 3500 3000 2500 2000 1500 1000

Absorbance / Wavenumber (cm-1) Paged Z-Zoom CURSOR

File #16 : ETOX_25T 4/13/2006 10:01 AM Res= .500

Ethylene oxide at 25 C, Composite spectrum (1 ppm-meter at 296 K)

0

10E-05

20E-05

30E-05

40E-05

4000 3500 3000 2500 2000 1500 1000

Absorbance / Wavenumber (cm-1) Paged Z-Zoom CURSOR

File #19 : CLETHO~1 4/13/2006 9:35 AM Res= .500

2-Chloroethanol at 25 C, Composite spectrum (1 ppm-meter at 296 K)

0

10E-05

20E-05

30E-05

40E-05

4000 3500 3000 2500 2000 1500 1000

Absorbance / Wavenumber (cm-1) Paged Z-Zoom CURSOR

File #18 : ETOHOH~1 4/13/2006 9:35 AM Res= .500

Ethylene glycol at 50 C, Composite spectrum (1 ppm-meter at 296 K)

EO Reference

Spectrum

ECH Reference

Spectrum

EG Reference

Spectrum

In situ Static Headspace FTIRIn situ Static Headspace FTIR

FTIR Static Headspace (SHS):

Outgassing Profile

FITR Spectra

Co

nce

ntr

atio

n

Ab

sorb

ance

Unit

s

Time

FTIR Static HS Gas Cell

Total Cumulative

Outgassing vs Time

SAMPLE

IR Source

IR Detector

FTIR Static Headspace (SHS):

Outgassing Profile

FITR Spectra

Co

nce

ntr

atio

n

Ab

sorb

ance

Unit

s

Time

FTIR Static HS Gas Cell

Total Cumulative

Outgassing vs Time

SAMPLE

IR Source

IR Detector

FTIR Static Headspace (SHS):

Outgassing Profile

FITR Spectra

Co

nce

ntr

atio

n

Ab

sorb

ance

Unit

s

Time

FTIR Static HS Gas Cell

Total Cumulative

Outgassing vs Time

SAMPLE

IR Source

IR Detector

FTIR Static Headspace (SHS):

Outgassing Profile

FTIR Static HS Gas Cell

Total Cumulative

Outgassing vs Time

FITR Spectra

Co

nce

ntr

atio

n

Ab

sorb

ance

Unit

s

Time

SAMPLE

IR Source

IR Detector

FTIR Static Headspace (SHS):

Outgassing Profile

FTIR Static HS Gas Cell

Total Cumulative

Outgassing vs Time

FITR Spectra

Co

nce

ntr

atio

n

Ab

sorb

ance

Unit

s

Time

SAMPLE

IR Source

IR Detector

Pebax Polymer Off-gassed (37C)

0

0.5

1

1.5

2

2.5

3

3.5

4

1 7 13 19 25 31 37 43 49 55 61 67 73 79 85 91 97 103

Data Points

ET

O C

on

ce

ntr

ati

on

(P

PM

v)

0 100 200 300 400 500 600 700 800

Minutes

0.0

20.0

40.0

60.0

80.0

ppm

Ethylene_Oxide

Equilibrium in CellEquilibrium in Cell

Simulated Use Simulated Use –– 24 Hr & 37 24 Hr & 37 ooCC

0 200 400 600 800 1000 1200 1400

Minutes

0.0

10.0

20.0

30.0

40.0

pp

m

Ethylene_Oxide

Rate Determinations (24 hrs & 37 Rate Determinations (24 hrs & 37 ooCC))

EO Release Rates

-10

0

10

20

30

40

50

0 50 100 150 200 250 300 350

Time (minutes)

EO

Co

ncen

tratio

n (P

PM

v)

1 to 5 hrs

5 to 10 hrs

10 to 15 hrs

15 to 20 hrs

20 to 24 hrs

Linear (1 to 5

DescriptionDescription 5 Hour5 Hour Release Release ExtrapolatedExtrapolated

MaximumsMaximums RateRate Simulated UseSimulated Use

PPMv/min

0.1506

0.1126

0.0973

0.0911

0.0917

µg/g

15.1

11.8

10.1

9.4

4.4

µg/g*24hr

69.6

52.1

45.0

42.1

42.4

Sum of [EO] 50.7Average [EO] 50.2

1 to 5 hours

5 to 10 hours

10 to 15 hours

15 to 20 hours

20 to 24 hours

Summary of ResultsSummary of Results

Simulated Use Test Simulated Use Test

ComparisonsComparisonsAnalytical Method

Extraction Time

Extraction Temperature

Number of Replicates

Concentration

Static Headspace GCFIDStatic Headspace GCFID

24 Hrs.24 Hrs.

37 37 ooCC

22

µµg/gg/g

SPME GCFIDSPME GCFID

24 Hrs.24 Hrs.

37 37 ooCC

33

µµg/gg/g

In Situ FTIRIn Situ FTIR

2 Hrs.2 Hrs.

37 37 ooCC

33

µµg/gg/g

Stainless Steel <5 <0.9 <0.7

Polypropylene/Pebax 21 ± 3 29 ± 7 ** 34 ± 11

Pebax 21 ± 1 30 ± 2 22 ± 0.3

Multi-Component Polymer 57 (1 Rep) 105 (1 Rep) 50 (1 Rep)

** 2 replicates were usedSPME Concentrations are estimated because different volumes were used between standards and extracts.

FTIR Static Headspace (SHS):

Outgassing Profile

FTIR Static HS Gas Cell

Total Cumulative

Outgassing vs Time

FITR Spectra

Co

nce

ntr

atio

n

Ab

sorb

ance

Unit

s

Time

SAMPLE

IR Source

IR Detector

Exhaustive Test ComparisonsExhaustive Test Comparisons

192192178178MultiMulti--Component PolymerComponent Polymer

52 52 ±± 2255 55 ±± 33PebaxPebax

< 0.7< 0.7< 0.9 < 0.9 Stainless SteelStainless Steel

2222Number of ReplicatesNumber of Replicates

14 Hrs.14 Hrs.5 Days5 DaysTime Required to Reach ExhaustionTime Required to Reach Exhaustion

1133Number of ExtractionsNumber of Extractions

InIn--situ FTIRsitu FTIRSPME GCFIDSPME GCFIDAnalytical MethodAnalytical MethodAnalytical Method SPME GCFID In-situ FTIRNumber of Extractions 3 1Time Required to Reach Exhaustion 5 Days 14 Hrs.Number of Replicates 2 2

Concentration µµµµg/g µµµµg/g

Method AdvantagesMethod Advantages

RealReal--time data collection allows time data collection allows

calculation of EO release rates (and ECH calculation of EO release rates (and ECH

formulation) formulation)

�� “tolerable contact” evaluations“tolerable contact” evaluations

FTIR method allows simultaneous data FTIR method allows simultaneous data

collection for materials characterization collection for materials characterization (ISO 10993(ISO 10993--18 )18 )

Method AdvantagesMethod Advantages

Since FTIR is additive, interferences can be Since FTIR is additive, interferences can be

subtractedsubtracted

EO/ECH/EG can be detected in a single test EO/ECH/EG can be detected in a single test using fewer devices for testingusing fewer devices for testing

Detection limits for EO are lower than GC Detection limits for EO are lower than GC

methodsmethods

Method AdvantagesMethod Advantages

Broad range of selectivity for detection of Broad range of selectivity for detection of

organic compoundsorganic compounds

Multiple spectral regions can be used to Multiple spectral regions can be used to quantify compoundsquantify compounds

Recent ASTM, NIOSH & EPA approvalsRecent ASTM, NIOSH & EPA approvals

--Method has been validatedMethod has been validated

ConclusionsConclusions

Demonstrated equivalency of simulated useDemonstrated equivalency of simulated use

Demonstrated equivalency of exhaustive testDemonstrated equivalency of exhaustive test

Confirmed ability to provide additional Confirmed ability to provide additional

informationinformation

�� Calculation of release ratesCalculation of release rates

�� Multiple test results on a single sampleMultiple test results on a single sample

�� Shorter test timeShorter test time

�� Quantification of other Quantification of other leachablesleachables

Industries using TechnologyIndustries using Technology

SemiSemi--conductor industry conductor industry

FluorochemicalFluorochemical manufacturing industrymanufacturing industry

Electronics industryElectronics industry

3M uses as standard test procedure for materials 3M uses as standard test procedure for materials characterizationcharacterization

Promulgated government standards:Promulgated government standards:�� ASTM D6348ASTM D6348--98 (Material Off Gassing D667098 (Material Off Gassing D6670--1 & 1 &

D5116D5116--97)97)

�� NIOSH 3800NIOSH 3800

�� EPA Method 320 EPA Method 320

Next StepsNext StepsCurrently performing IQOQ on equipmentCurrently performing IQOQ on equipment

Validating test method for the analysis of Validating test method for the analysis of

EO/ECH/EGEO/ECH/EG

Publishing in scientific journal within a yearPublishing in scientific journal within a year

Evaluate & develop other applicationsEvaluate & develop other applications

�� Currently validating a method for the analysis Currently validating a method for the analysis of water content in polymers to assist with of water content in polymers to assist with establishing manufacturing specificationsestablishing manufacturing specifications

COMMENTS & QUESTIONS?COMMENTS & QUESTIONS?

Cost Analysis of FTIR vs. SPMECost Analysis of FTIR vs. SPME

Capital equipment cost ~ $100,000Capital equipment cost ~ $100,000

Operator skill level Operator skill level –– chemist with FTIR chemist with FTIR experience desiredexperience desired

Supply costs Supply costs –– less than GCless than GC

Maintenance costs Maintenance costs –– similar to GCsimilar to GC

Space required Space required –– similar to similar to GCw/oGCw/o

extraction spaceextraction space

Total cost Total cost –– competitive with GCcompetitive with GC