The Uses of Portable
FT-IR Spectroscopy
in the Power
Generation Industry
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Jim Fitzpatrick
Mobile FT-IR Product Specialist
Agilent Technologies, Inc.
July 16, 2013
Spectroscopy
“Spectroscopy” is the study of how electromagnetic radiation interacts with the atoms
and molecules that compose matter
“Infrared” spectroscopy is specifically the study of how infrared light (heat) is
absorbed by the bonds between atoms that form molecules
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A spectrum is a graph of how much infrared light is absorbed
by molecules at each wavenumber of infrared light
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Peaks appear where sample
absorbs light
Infrared
(heat)
Source
Infrared
Detector
2
Hexane
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H – C – C – C – C – C – C – H
H
|
H
|
H
|
H
|
H
|
H
|
|
H
|
H
|
H
|
H
|
H
|
H
C – H stretch
H – C – H bend
Ab
so
rban
ce
Wavenumber (cm-1)
Hexanol
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H – C – C – C – C – C – C – O – H
H
|
H
|
H
|
H
|
H
|
H
|
|
H
|
H
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H
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H
|
H
|
H
C – O stretch O – H stretch
Ab
so
rba
nc
e
Wavenumber (cm-1)
What role can FT-IR play in the
Power Generation Industry?
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FT-IR
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Infrared has been an
established method for
over fifty years
Relegated to laboratories
due to
• Its large size
• Complexity of use
• Expensive
• Generates data and not
actionable answers.due
to
• Its large size
Mobile FT-IR
•Agilent has pioneered the
introduction of portable
spectrometers
•Comparable results to
laboratory spectrometers
•Field-ruggedized for non-
ideal conditions
•Intuitive, actionable answers
•Methods driven software –
expert user not required
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Analysis of Lubricants
- Lubricants protects parts, inherent part of a machine (without it, the machine does not function
properly) and prevent premature system/ machine failure
- Lubricants have a finite life (determined by certain specifications) beyond which they do not perform their role.
- Without a proper lubrication management program, lubricated machines and engines see their operating costs and maintenance costs skyrocket
- FT-IR spectroscopy can easily determine if an oil is fit for function or not
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Causes of oil failure
The most common cause of failure of lubricating oil is oxidation.
Oxidation is caused by:
• Heat
• Extreme Pressures
• High sheer conditions
• Water – Accelerates oxidation by forming peroxides
– Can cause wash out of antioxidants and other additives
• Metal wear particles – Acts as a catalysts that accelerate oxidation
• Electrostatic sparking – Introduces nitrates
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Early detection of oxidation in oil is critical to
the success of any preventative maintenance
program
Oxidation
• Oxidation is a chemical change within the lubricating oil that significantly lowers it
lubricity and shortens remaining useful life.
• It is critical to extend the life of the lubricating oil and to minimize oxidation. This is
done with the use of anti-oxidants
• Aminic and Phenolic Based Additives are sulfur based –
- They function as preservatives to prevent oxidation and to inhibit the
oxidation mechanism
- Will not reverse oxidation damage
- Once they are consumed, consumed oxidation skyrockets
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Infrared Spectrum of Oil
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Phenolic
Antioxidant Water/
Amine
Antioxidant
Various Oxidation/
Nitration Products,
and Additives
Demulsifying
Agents, Rust
Inhibitors, Foam
Suppressants,
And Antioxidants
Hydrocarbon Oil Backbone
3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600
2.0
1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
Wavenumber
Measuring Anti Oxidants in Turbine Oil
R
O H
R
O H
N
H
R R
N
H
R R Phenolic DBPC,
di-tertiary-butyl
paracresol
3680 3675 3670 3665 3660 3655 3650 3645 3640 3635 3630 3625 3620 3615 3610 Wavenumber
Absorb
ance
3680 3675 3670 3665 3660 3655 3650 3645 3640 3635 3630 3625 3620 3615 3610 Wavenumber
Absorb
ance
3460 3455 3450 3445 3440 3435 3430 3425 3420 3415 3410 3405 3400 3395
Absorb
ance
3460 3455 3450 3445 3440 3435 3430 3425 3420 3415 3410 340
5
3400 3395
Wavenumber
Absorb
ance
Aminic aDPA, alkyl di-phenylamine
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Phenolic/Aminic Antioxidants in Turbine Oil
3700 3690 3680 3670 3660 3650 3640 3630 3620 3610
Wavenumber
Ab
so
rba
nce
Peak Area
1
4
7
10
13
16
19
22
25
28
Quant Validation Plot for Phenolic (ppm) R²=1.000
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
10000
9000
8000
7000
6000
5000
4000
3000
2000
1000
0
Concentr
atio
n
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Typical Oil Monitoring Graph (applicable to all
sorts of Oil)
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Water – The tribologists nemesis
Water Contamination in power generation turbines causes premature failures • Loss of physical properties of the oil
–Viscosity –Specific Gravity or Density –Surface Tension –Cohesion and Adhesion properties
• Oil loses its ability to coat, lubricate, and protect critical
clearances
• Water accelerates additive depletion and oxidation mechanisms
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Water in oil – A difficult measurement
Why is it so hard to measure water in oil?
• Lack of Homogeneity
– Water forms micelles in oil
– Water adheres to container walls
– Separates out quickly (demulsifiers present)
– Forms layers
– Water droplets are attracted to each other
and air bubbles
• Water evaporates into container head space after mixing
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Problems with Water Measurement
Water in mineral oil forms small, irregular droplets
Droplet can scatter the light
Scattered light shifts baseline and reduces absorbance
Water stabilization method makes droplets uniform and small
I
R Detector
Scatter
Large droplets => IR scattered
I
R
Detector
Small droplets => IR absorbed
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Water Measurement Comparison
turbine oil water.tdf ,105 (R² = 0.859309544)turbine oil water.tdf ,105 (R² = 0.859309544)
Actual Concentration ( C1 )Actual Concentration ( C1 )
Pre
dic
ted
Co
nce
ntr
atio
n (
F1
1 C
1 )
Pre
dic
ted
Co
nce
ntr
atio
n (
F1
1 C
1 )
-400
200
800
1400
-100 200 500 800 1100 1400 1700
-400
200
800
1400
-100 200 500 800 1100 1400 1700
91
92
93
94
103
104105
106
107
118
119
120
121
122
133
134
135
136
145
146147
148
158
159
160
161
172
173
174
175
185
186187
188
199200201
202
211212213214
224
225
226
227
238239
240242
253254
255
256
265
266
267
268
277
278
279
280281
294295
296297
306
307
308
-400
200
800
1400
-100 200 500 800 1100 1400 1700
300ppm span
500ppm
span
4000 2600 1600
Absorb
ance
Water OH
stretch
Conventional Method
1127.5
0.3
136
4000 3400 2600 1600
Absorb
ance
turbine water surf actant.tdf ,25 (R² = 0.998029969)turbine water surf actant.tdf ,25 (R² = 0.998029969)
Actual Concentration ( C1 )Actual Concentration ( C1 )
Pre
dic
ted
Co
nce
ntra
tion
( F
4 C
1 )
Pre
dic
ted
Co
nce
ntra
tion
( F
4 C
1 )
-500
1000
2500
4000
5500
-500 1000 2500 4000 5500
-500
1000
2500
4000
5500
-500 1000 2500 4000 5500
12345678
9101112
13141516
17181920
2122
2324
252627
28
2931
32
33343536
37383940
41424344
45
46
4748
49505152
545556
57585960
61
6364
666768
-500
1000
2500
4000
5500
-500 1000 2500 4000 5500
A2 Water Stabilizer method produces a more sensitive, reproducible result.
Stabilization Method
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PAL Predictions: Water in Turbine Oil w/
Surfactant Stabilizers
PAL (ppm) KF (ppm
Difference
(ppm) % Error
525 504 21 4.2
1052 965 87 9.0
2027 2002 25 1.2
2914 2838 76 2.7
4835 4753 82 1.7
Analysis performed in less than 1 minute
Usefulness of FT-IR for oil analysis
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Method Types Turbine Oil – • Mineral Oil • Synthetic
Hydraulic Fluid • Mineral Oil • Polyol Ester Synthetic • Phosphate Ester Synthetic
Gear Oil – • Mineral Oil • Mineral Oil / Synthetic
Engine Oil • Mineral Oil • Synthetic
Components Water Anti-Oxidants
Phenolic Quantitative 150 to 5000 ppm
Aminic Quantitative 150 to 5000 ppm
Oxidation Additives
Antiwear Extreme Pressure
Soot Quantitative 0 – 3 %
FT-IR provides an early warning on oil failure based on chemical changes within the oil
FT-IR Spectroscopy - Operation
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Single Transmission Cell Operation
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1. Place Sample
on lower Window 3. Analyze the sample
2. Rotate into
place 4. Cleaning is
easy!
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Easy-to-understand results
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Petrochemical - Oil Methods
Gear ASTM 2412 EP Fluid Mineral
DTE PM 220 Mineral
EP 460 Mineral
Spartan EP 220 Mineral
Terrestic 220 Mineral
Duolec LE 1606 Iso 320 Mineral
Duolec LE 1607 ISO 460 Mineral
Mobile 600 XP ISO 460 Mineral/Synthetic
Mobile SHC 220 Mineral/Synthetic
Mobile SHC 636 ISO 680 Mineral/Synthetic
Mobile SHC 636 ISO 68 Mineral/Synthetic
Royal Purple Synfilm 220 Mineral/Synthetic
SL 150 Mineral
SL 220 Mineral
SL 320 Mineral
SL 460 Mineral
Hydraulic ASTM 2412 Polyol Ester Synthetic/ Polyol Ester
Calpar 150 Mineral
Mobile DTE (24, 25, 26) Mineral
EHC (Fyrquel) Phosphate Ester
Exxon Nuto 68 Mineral
Hitachi HN 46 Mineral
Cheveron H46 Mineral
HyGuard Mineral
Quinplex White LE 4010 H1 ISO 46 Mineral
Quinplex White L4030 H1 ISO 100 Mineral
Monolec LE 61110 ISO 46 Mineral
Royal Purple Synfilm GT 100 Synthetic/ Mineral
Quintolub 822-300 Synthetic Polyol Ester
Quintolub 888-68 Synthetic Polyol Ester
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Turbine
Busch Mineral
Monolec LE 6404 ISO 100 Mineral
Royal Purple Syndraulic ISO 32 Synthetic/ Mineral
Exxon Terrestic GT 32 Mineral
Turbine Oil Mineral
Chevron GST Mineral
Engine ASTM 2412 Crankcase Mineral
Crankcase Oil (A2 Method) Mineral
Military Oil Mineral
Rotella T 15w40 Mineral
Mobile 1 Synthetic
Transformer
ASTM D2668 - Antioxidants
Compressor
Monolec LE6403 ISO 68
Crude
Water in Crude Oil (0 - 1%)
Water in Crude Oil (0 - 80%)
Other
Antifreeze in water
Water in ethanol
Oil in water (0 - 30 ppm)
Petrochemical - Oil Methods (cont.)
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Detects common contaminations of oil
• Phosphate ester (EHC) hydraulic in turbine, gear, or mineral based hydraulic fluids – “Fingerprint” IR bands for EHC
– Cross contamination from filtration & dehydration units
• ID and/or Quantify a range of impurities
–WD-40 in Hydraulics
–High particulates like Soot, Dirt, and wear metals
Contaminant Detection By FT-IR
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Environment – Oil in Water
High solids in water requires solvent extraction
•Process waters from offshore oil drilling
•Accidental oil spills
•Harbor water cleanup
•Waste water regulation
Low solids in water can be done with
non-solvent filtration system and FT-IR
•Closed loop turbine cooling water
Good for medium to heavy oils
•Not as good for light
hydrocarbons (i.e. BTEX)
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Environment –
Oil in Water by Extraction
•Oil in water a key environmental measurement
•FT-IR measurement by Extraction
– Historically extracted by Freon 113 (ASTM D3921)
– Currently extracted by S 316 (ASTM 7066-04)
– Also extracted by cyclohexane in ASTM D7678
•Oil measured directly in extracted fluid using Transmission
•Agilent 4500/5500 DialPath makes measurement easy
– Easy to clean liquid cell
– Reproducible path length
– Easy to use software
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Environment – Oil in Water by Cyclohexane
Extraction (ASTM D7678)
• Previous Freon FT-IR extraction method is being phased out
- Freon and other halogenated solvents have been banned by the Montreal
protocol due to their ozone depleting activity
• Cyclohexane is a CFC-free non-ozone depleting solvent
• Agilent’s FT-IR version of the ASTM D7678 features a limit of quantification
(LOQ) of .75mg/L (0.75ppm) oil in water
• Standard procedures for liquid-liquid solvent extraction remain unchanged from
previous ASTM methods.
• These ASTM D7678 based FT-IR results will correlate to other methods
- ASTM D3921, D7066, ISO 9377-2, EPA 413.2, and 418.1 methods
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Simple 5 step process –
1. Add Cyclohexane
Add 20mL of cyclohexane to 900mL of process water and vigorously
shake for 2 minutes.
2. Remove Top Layer
Allow layers to separate, and remove the top layer for analysis
3. Add Cleaning Agents
Add 2g drying agent (sodium sulfate) and 2g Florisil™ to the cyclohexane
extract, shake vigorously, and allow to settle for 2minutes.
4. Filter Cyclohexane Extract
Filter the “cleaned” cyclohexane with a 0.45um nylon syringe filter (17mm).
5. Measure FTIR Spectrum
Add the cyclohexane to the Dialpath™ or TumblIR™ cell and initiate the FTIR
scanning. The result will be displayed after 30seconds of scanning.
Environment – Oil in Water by Cyclohexane
Extraction (ASTM D7678) Simplified Procedure
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The automatically obtained data results from the MicroLab software for the
4500series and 5500series FTIR spectrometers.
This result is from a validation standard of 9.3mg/L mineral oil and 5mg/L
vegetable oil in fresh water, then extracted with 20mL cyclohexane and filtered.
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The mineral oil in cyclohexane calibration plot of actual (x-axis) vs. predicted
(y-axis) values. The values displayed are the final concentrations of oil in water
based on the ASTM D7678 parameters (900mL water, 20mL cyclohexane).
Oil Calibration Set
Standard Name Oil (mg/L)
OIW Soln A 0.00
OIW Soln B 0.05
OIW Soln C 0.15
OIW Soln D 0.26
OIW Soln E 0.84
OIW Soln F 1.70
OIW Soln G 2.54
OIW Soln H 4.20
OIW Soln I 8.30
OIW Soln J 16.54
OIW Soln K 24.90
OIW Soln L 32.55
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Fuel Analysis By FT-IR
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Petrochemical - Fuel Methods
In addition to oil analysis, FT-IR can be used to determine fuel quality parameters. • Water Contamination
– Gasoline – Diesel
• Gasoline contamination in diesel
• Gasoline performance characteristics
– Oxygenates, RON, MON, Aromatics
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Method Name Fuel Type Sample Interface Components Range
Fuel - Gasoline Analysis PAL Gasoline TumblIR MTBE 0.25-16.5 vol% ETBE 0.25-16.5 vol%
Ethanol 0.1-16.5 vol% Total Aromatics 0.5-45 vol%
Total Olefins 2-12 vol% Benzene 0.2-2.5 vol% Toluene 0.5-25 vol%
RON 85-97 MON 80-86 Water Relative
Fuel - Gasoline Water Analysis Gasoline TumblIR Water 150-6000ppm
Fuel - Water in Diesel Stabilized Diesel TumblIR Water 100-4000ppm
Oxidation Relative Fuel - Water in Gasoline (0-80%) Stabilized Gasoline TumblIR
Water 0 - 80 vol% Fuel - Gasoline in Diesel Version3 Diesel TumblIR
Gasoline 1000-20000ppm Oxidation Relative
Antioxidant 150-10000ppm
Petrochemical - Fuel Methods
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Gasoline in Diesel Fuel
Gasoline fuel contamination in diesel fuel causes engine failures
-- Causes coke formation on fuel injectors, and excessive wear on fuel contact
parts
-- Problem is worse in Ultra low sulfur diesel (ULSD) engines
Much less lubricity than off-road, agricultural or older diesel formulations
Sulfonated hydrocarbons are removed in ULSD
Gasoline can wash varnish deposits into the engine
Lowers the diesel cetane value or energy content
Manufacturers want proof of no gasoline in diesel for warranty engine repairs
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Gasoline, 87 Oct
Diesel
Gasoline in Diesel Fuel
Wavenumber
3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
Absorb
ance
Ethanol Light
Aromatics
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1150 1100 1050 1000 950 900 850 800 750 700
0.60
0.55
0.50
0.45
0.40
0.35
0.30
0.25
0.20
0.15
0.10
0.05
0.00
-0.05
Wavenumber
Ab
so
rba
nce
Ethanol, Gasoline
Diesel Aromatics
Toluene,
Gasoline
Benzene, Gasoline
0.0% Gasoline
0.5% Gasoline
1.5% Gasoline
3.0% Gasoline
5.0% Gasoline
Gasoline in Diesel Fuel
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Biodiesel Analysis
Increased use of Biodiesel. Many countries allow or require biodiesel in regular diesel Some states allow up to 3% biodiesel in diesel without disclosure
Biodiesel is not appropriate for all fuel uses
Can clog filters, reduce cold weather performance, or cause problems with storage Need exists to measure biodiesel for 2 different goals
Monitor % biodiesel for blending B5, B10, B50 Regulatory and compliance
Monitor low levels of biodiesel as a contaminant 0.025% to 20%
Regulatory methods specify FTIR
EN 14078 : 2009 Transmission Liquid Cell ASTM D7371-07 Mulitple Reflection ATR
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Petrochemical - Biodiesel Methods
Method Name Components
Fuel - Biodiesel % in Diesel Version4.a2m Biodiesel 0.025% – 1%
*requires 5500t/4500t Biodiesel 1% - 10%
Biodiesel 10% - 20%
Interference – water vapor
Interference – diesel oxidation
Fuel - Biodiesel ASTM D7371-07 Version3.a2m Biodiesel 1% - 10%
*requires 5500/4500 w/9 reflection ATR Biodiesel 10% - 30%
Biodiesel 30% - 100%
Fuel - Biodiesel EN 14078 Version3.a2m Biodiesel 0.5% -20%
*requires 5500t/4500t Peak area @ 1745 cm-1
Fuel - Water in Diesel Version4.a2m Water in diesel 100 ppm – 900 ppm
*requires 5500t/4500t Water in diesel 900 ppm –3000 ppm
*requires Water in Oil Surfactant Kit Diesel oxidation
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Agilent 5500a Multibounce FT-IR
ASTM D7371-07 Biodiesel in Diesel (1-100%)
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Material Verification /Degradation
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Hand Held FTIR Material Identification Germanium ATR
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•Selectivity of FT-IR is ideal for material
identification.
•Well suited to polymers and elastomers
•Ge ATR ideal for carbon filled materials
•Industrial need for positive ID
•O-rings and seal materials
•Safety requirement to prevent leaks
•Compatible with the use of XRF for pipes
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Exoscan can identify all 10 groups of seals Fluorosilicone, Silicone, Viton, EPR/EPDM, Neoprene, Butyl, Kalrez, NBR,
Polyurethane, Natural Rubber
Easy Identification by spectral search Similarity = correlation
Highest correlation = correct ID
Demonstration 15 samples provided by Material Research Society
Exoscan correctly identified all samples
Only one sample had a close second match
Hand Held FT-IR Material Identification O-ring and Seal Identification
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Cable Degradation Analysis
Cables in a nuclear power plant are submitted to a variety of environment stressors
Heat,
Humidity,
Steam,
Dust,
Oil,
UV exposure,
Radiation.
The protective jacket made from XLPE, EPR, Hypalon, EPDM etc are losing their
original properties
Insulating power,
Mechanical properties.
Hand-held FT-IR provides a means for non-destructive cable analysis in the field.
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Degradation at elevated temperatures over time
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