Atlas Online Weathering Academy 5 Correlation Acceleration 2017-06-14

ns
t i o
u
Atlas Online Weathering Academy
o l
S
n g
t i
e s
l T
r i a
t e
a Fundamentals of Weathering:
M
a s Part 5 – Acceleration and Correlation
t l Atlas Online Seminar

A June 13/14, 2017
s
Presenter
o n
Allen Zielnik (Chicago, USA)
t i
u
 Senior Consultant – Weathering Science
 Global Weathering Applications Manager
o l
 Product Manager –Corrosion & Flammability
S
n g
Al.Zielnik@Ametek.com
t i
e s
Background:
l T
Engineering (1975)
r i a
- Degrees in Analytical Chemistry (1973) and Electronics
t e
- 18 years with analytical scientific instrument companies
a
- 24 years with Atlas in weathering and polymer analysis
presented M
- Over 140 published works and conference presentations,
a s over 250 career long educational technical seminars
t l
A
www.atlas-mts.com 1
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Outline
o n
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Introduction of Atlas
u t
l
Acceleration and Correlation
- Calculation of test durations
So
g
- Basic principals of acceleration
i n
- Statistical quantification of correlation
Summary
st
Question and Answers
Te
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Upcoming Seminars and Events
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at
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www.atlas-mts.com 2
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Who are we?
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102 years of weathering testing innovation
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Weathering & Corrosion Instruments Outdoor & Lab Weathering Services
S o
n g
t i
e s
l T
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Atlas Custom Systems Consulting, Client Education and
r i
Larger scale solar simulation Standards
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Failure Testing
Modes?
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Design Risk? Evaluate
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Climates Materials
Durability
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Specs
Test Set
t la
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www.atlas-mts.com 3
ns
t i o
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So
n g
t i
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Acceleration and Correlation
a l
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Fundamentals of Weathering – Part 5
t e
a
M
a s
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Correlation of Test with Real-World
o n
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S o
n g
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Can I get this . . .r
t e
a
M
a s
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A
. . . by doing this?
www.atlas-mts.com 5
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Frequent question:
o n
t itest”
u
What is the acceleration between “xenon
l
and “outdoors”? o S
n g
t i
?es
l T
r i a
t e
a
M
a s
t l But . . . how good is the correlation?
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www.atlas-mts.com 6
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Fast test . . . . But poor correlation?
o n
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Coin Toss Method alternative*:
• Faster
S o
g
• Cheaper
i n
• Right about 50%
t
of the time
e s
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Before you ask . . .
a l • Not an ISO, ASTM, etc. standard
i
• Calibrated coin not available from Atlas . . .
er
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a s
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www.atlas-mts.com 7
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Calculation of Test Durations
o n
Question: How long should I test to simulate 12 months
t i
Sanary-sur-Mer (France)?
lu
S o
g
Radiation data:
Wavelength range 295 – 800 nm
t i n
295 – 400 nm 340 nm
s
Annual Radiant
e
2701 MJ/m² 295 MJ/m² 2.5 MJ/m²
Exposures
l T
a
Weathering test in Xenon-arc instrument (ISO 4892-2; Method A)
Irradiance
r i 550 W/m² 60 W/m² 0.51 W/m²
t e How long should I test to achieve the

a as in one year in Sanary-sur-Mer?
Question (simplified):
M
same radiant exposure
a s
l
Note: The Spectral Power Distribution (SPD) measured locally and in the laboratory
t
instrument should match as closely as possible.
A
www.atlas-mts.com 8
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“Acceleration Factor” v. Acceleration Factor
o n
t i
lu
The time required in a specific outdoor
So
weathering test to induce a certain specific property
n g
i
change in a specific specimen, divided by the time
st
needed for the same change in a replicate
e
specimen in a specific accelerated laboratory (or
T
outdoor) weathering test.
a l
r i
t e
Exposure Time Outdoor
a = AF
M
Exposure TimeAccelerated
a s
t l
A
www.atlas-mts.com 9
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Weathering Tests
o n
t i
lu
Original property
S o
n g
i
Acceleration factor :
AF s
t
e
Property change
= t / taccelerated
T
Service life outdoor
a l
r i
e
Fail
t
limit
a
M
s
Accelerated
a
weathering
t l
taccelerated. toutdoor ExposureTime
A
www.atlas-mts.com 10
s
Time Compression
o n
t i
lu
Time compression by keeping test parameters constantly
at maximum natural intensity.
S o
n g
t i
s
Course of three normal days of outdoor sunlight
T e
l
E (W/m²) , T (oC)
r i a
t e Natural max
a
M Natural
a s
t l Time
A
8 14 20 02 8 14 20 2 8 14 20
s
Acceleration: Overstress
o n
t i
lu
Acceleration by keeping test parameters constantly higher
than maximum natural intensity.
S o
n g
t i
s
Course of a normal day outdoor
T e > Natural max
l
E (W/m²) , T (oC)
r i a
t e Natural max
a
M Natural
a s
t l Time
A
8 14 20 02 8 14 20 2 8 14 20
ns
t i o
lu
So
n g
Examples of Acceleration
t i
s
Factors
e
l T
i a
Asr
t e reported in the literature
a
M
a s
t l
A
Time Compression and Correlation
ns
t i o
Example 1
lu
• Material: Metallic base coat
(VW, Audi, Skoda, Seat)
S o
• Criterion:
n g
i
Color change, chalking, gloss
• Ci Weather-Ometer
st
• 55 W/m² (300-400 nm), 63 ºC BPT,
Te
l
50 % RH;
a
Cycle 20/10
r i
Correlation to outdoor weathering in Florida, Europe and Kalahari
t e
(over 22 years of 2-5 year studies) was good.
Lab Acceleration factor:
a
M
- vs. Florida: 4X
s
- vs. Europe: 27 X !!!!
t la - vs. Kalahari: 9 X !!
A
s
o n
t i
lu
o
Example 2
S
• Material: Paints and varnishes
g
for indoor and outdoor
n
• Criterion: Color change
• Method:
t i
ISO 11341 (replaced by ISO 16474-2)
e s
T
60 W/m² (300-400 nm), 65 ºC BST,
l
38 ºC CHT, 40-60% rel. humidity,
a
Cycle 102/18
r i
t e
Correlation to outdoor weathering
a
in Florida, Europe good
M
a s - vs. Florida: 6X
t l - vs. Central Europe: 20X !!!
A
s
o n
t i
Example 3
lu
• Material:
Colored Pigment Paint
S o
n g
• Xenotest
t i
• Method: ISO 11341
e s
T
(replaced by ISO 16474-2)
l
60 W/m² (300-400 nm),
a
65 ºC BST, 38 ºC CHT,
40-60% rel. humidity,
r i
e
Cycle 17/3
a t
Correlation to Outdoor Weathering in Florida good
M
s
a
- vs. Florida: 9X !
t l
 General statement: 1 year Florida = 1000 h in instrument
A
s
o n
t i
lu
o
Example 4
• Material: Geotextile
S
• Criterion:
n g
50% Reduction Tensile Strength
t i
• Method: ASTM D4355
e s
T
0.35W/m² (340 nm) , 65 ºC BPT,
l
38 ºC CHT, 50% rel. humidity,
i a
cycle 90 / 30
Correlation to outdoore
r
t
afactor:
weathering in El Paso Texas
M
Lab Acceleration
s
- vs. El Paso (Texas) 4.3X
t la
A
s
o n
t i
Example 5
lu
• Material: Coloured Textiles
S o
g
• Method: ISO 105-B02
t i n
s
42 W/m² (300-400 nm),
e
Window glass filter,
T
50 ºC BST, 40% rel. humidity
a l
i
Correlation to outdoorrweathering in central Europe good
t e
a
M- vs. central Europe:9X (~2X over Florida)
a s
t l
A
s
Acceleration factor variability
o n
Region Accelerated Xenon-arc Weathering
t i
Calculated “acceleration
lu
o
Experimental acceleration
S
factors” (based on factors - reported values
annual radiation) (see previous examples)
n g
i
Central 8.8 27 20 9
t
Europe
Sanary 6.4
e s
(South
l T
a
France)
Florida
r i5.3 4 6 9 4
Arizona
t e 4.3
a 4.8
M
Kalahari 9
s
Deviation from calculated and measured factors 
a
t l
“Real acceleration factors” depend on: reference location,
A test conditions and the material!

s
o n
Summary:
t i
l
• Test methods using test conditions at maximumu
S o
natural intensities often show good correlation
n g
i
• Spectral irradiance, relative humidity, temperature,
s t
time of wetness influence degradation
e
 Search for optimum weathering cycles
Tmaterial specific
• Acceleration factors l
a
are
 There are NOi“universal”
r
correlationeor acceleration factors
at
M
a s
t l
A
ns
t i o
lu
So
n g
ti
Accelerated Testing:
s
Te
Intensification
a l (Overstress)
r i
t e
a
M
a s
t l
A
Acceleration
ns
“ I do not have the
t i o
time. lu
Can I accelerate my So
testing? “
n g
t i
e s
l T
r i a
t e
a
M
a s
t l
A
s
Intensification (Overstress) for acceleration
o n
t i
lu
So
n g
t i
e s
l T
r i a
21 days at e
37°aCt
4 minutes at
M
175 ° C
a s
t l Results can be surprising…
A
s
Acceleration – Experimental Approach
o n
i
Intensification (Overstress) of one or more weather
parameters:
u t
- Radiation
o l
• Level of spectral irradiance
S
g
• Short wavelength radiation (below natural UV-cut on)
n
- Temperature
t i
s
• Level of temperature
• Temperature cycles
Te
l
- Moisture
i a
• E.g. dry/wet cycles (amplitude/frequency)
r
Note:
t enatural level require validation
Test methods with test conditions above the
a studies):
maximum
M increased irradiance
(reciprocity
- la
s
- Common:
A t Uncommon: increased irradiance + increased temperatures
s
Intensification of Irradiance
o n
Law of Reciprocity H=Ext
t i
lu
Reciprocity is given, if the same amount 1 sun
o
of radiant exposure (H) causes the 1
S
same amount of photochemical
g
damage (or property change) no matter
n
1 sun
over which time (t) it is applied.
i
2
st
E (W/m²)
Reciprocity Law
e
(Bunsen, Roscoe 1859):
T
1 sun
l
3
E x t = constant
r i a
for a given photoresponse
3 sun
t e
a
Limitations of Reciprocity 4 always same damage
M
All other reaction parameters (temperature, → Reciprocity obeyed
s
humidity…) must be the same.
la
Other reaction steps (like oxygen diffusion) Time
t
must not be a factor in determining rate Want to know more? Look up
A
Schwarzchild’s reciprocity “p” factor]
www.atlas-mts.com
s
Example 1: Increased Irradiance
o n
ISO/TS 19022:2014-03-28 – Plastics –
t i
u
Controlled acceleration of laboratory
weathering by increased irradiance
o l ORWET Orange
S
coatings exposed
Procedure to validate reciprocity: in a Xenotest®
g
Alpha at different
n
irradiance levels
i
Test at the lowest
1 according to
t
irradiance level ISO 4892-2
s
without rain cycle.
e
Test at increased
2
T
irradiance levels
a
Keep all other test parameters constant!
l
r i
Plot test results as y = 0.2516x - 1.0463
e
R² = 0.9867
t
3 function of radiant
a
exposure  Good
M
Reciprocity
Calculate the deviations
4
a s from a fit of the data
t l
A
e.g. a good Pearson correlation coefficient should be > 0.9
s
o n
• Material: High visibility yellow on Polyester-Textile
t i
• Criterion: Colour change method: ISO 105-B02
lu
48 °C BST, 33 °C CHT, 40% rel. humidity
S o
Irradiance (300-400nm): 42 W/m², 84 W/m²
n g
Reciprocitystudy
Reciprocity studyon
onaayellow
t i
yellowhigh-visibility
high-visibilitydye
dyeon
onPolyester
Polyester
s
(Instrument:Xenotest
(Instrument: XenotestAlpha+)
Alpha+)
e
25
20
l T
i a
delta E*
r
15
t e Reciprocity very
a
42 W/m²
10
84 W/m² good!!
M
s
5
t la 0
A
0 5 10 15 20 25 30
Radiant Exposure [MJ/m²]
s
o n
t i
Material: Polyamide- and Polyester textiles for automotive interiors
u
100 ºC BST, Irradiance E (300-400nm) at 47 W/m² and 141lW/m²
Criteria: Colour change; Method: VDA 75202;
Radiant exposure: H (300-400 nm) = 13,200 kJ/m²

S o
Test duration: (47 W/m²) = 78 h
n g
(141 W/m²) = 26 h
t i
4,5
e s
47 W/m2 141 W/m2
T
4
l
3,5
a
Color change ΔE
i
3
r
Reciprocity
e
2,5
very good!
t
2
a 1,5
M
1
s
0,5
t la 0
PA 26 PA 17 PA 18 PA 8 PA 10 PA 12 PES 5 PES 13 PES 16
A
(grey) (dark (marine (blue) (green) (light (dark (brown) (olive)
green) blue) blue) green)
Fluorescent UVB vs. Sunlight
ns
t i o
lu
S o
n g
t i
e s
l T
r i a
t e
a
UVB-313 is still in many test methods, but not recommended by the guidance standards:
M
ISO 4892-1 & ASTM G151: Factors that may decrease correlation: Short wavelength
s
exposure
la
ASTM G154/ISO 4892-3/ISO 16474-3: With the use of UVB-313 fluorescent lamp, the
t
degradation of materials can be unrealistic…
A
s
Example 1: Lower Wavelength UV
o n
i
PVC (example):
u t
o l
S
Florida Exposure Xenon-arc Filtered Fluorescent UVB
FloridaFlorida Exposure
Exposure Xenon-arc Filtered
Xenon-arc Daylight Filter Fluorescent UVB-313
Fluorescent UVB
g
1.2
1.2 1.2
1.2 1.2
1.2
AA AA AA
n
BB BB
i
BB
11 11 11
st
ΔOD at 1780 cm-1
ΔOD at 1780 cm-1

0.8 0.8
ΔOD at 1780 cm-1
ΔOD at 1780 cm-1

0.8 0.8
ΔOD at 1780 cm-1

0.8
e
0.8
ΔOD at 1780 cm-1

T
0.6
0.6 0.6
0.6 0.6
0.6
0.4
a
0.4
l
i
0.4 0.4 0.4
0.4
er
0.2
0.2 0.2
0.2 0.2
0.2
at
00 00 00
00 5000
5000 10000
10000 15000
15000 20000
20000 00 1000
1000 2000
2000 3000
3000 4000
4000 00 1000 2000 3000
1000 2000 3000
M
Time inin
Time Hours
Hours Time inin
Time Hours
Hours Tim eeinin
Hours
Tim Hours
 HarshsUVB-313 test leads to reversal of ranking

t la
A
s
Example 2: Lower Wavelenghth UV
o n
9 Polyester coatings – brown color
t i
lu
S o
n g
t i
e s
l T
i a
Fail
er
at G.R. Pilcher (2001)
cited in:
M
Geburtig et al.
s
4.EWS, 2009.
t la
A
Unrealistic UV cut-on or unrealistic SPD seldom results in good correlation
s
Arrhenius Equation for Photochemical Reactions
The modified Arrhenius equation describes the influence of temperaturen

t i o on
lu
the reaction rate of photochemical degradation processes:
S oSchematic diagram of the potential

energy of a photochemical reaction:
g
E a

k  AE e 
i n
Transition State
RT
t
Ea
Relative Potential Energy

e s
T
Excited State
Absorption
l
where k is the reaction rate constant of the process
a
A is an Arrhenius pre-exponential factor
i
Ea is the apparent activation energy (in J.mol-1)
r
R is the gas constant (8.314 J.mol-1·K-1)
e
T is the absolute temperature (in K)
t
α is a material specific coefficient Ground State
a
E is the effective irradiance (in W·m-2) of Educts
Decomposition
M
Products
a s
l
• The reaction rate depends on effective irradiance and temperature
A t
• “Rule of Thumb”:
Temperature increase of 10 K leads to doubling of degradation rate
s
Temperature Dependency
o n
t i
u
Hi Ea, large temperature effect
o l
Theoretical acceleration of coating
S
photo-degradation at 2 suns and
g
different temperatures over
i n
natural conditions (1 sun, 25 °C)
st Low Ea, little temperature effect
Te
a l
r i
Hinderliter et al. ECS Transactions, 24 (1) 1-26 (2010)
t e
Acceleration depends on temperature and activation energy!
a is often unknown
M of Thumb” Most often disobeyed!!!
Activation energy
Note:ainsweathering often a 20-30% increase of the reaction

General “Rule
t lis observed by a 10K increase

A
rate
s
Temperature Effects: Acceleration
o n
Arrhenius Concept:
t i
The reaction rate of photochemical degradation processes depends on the effective
lu
irradiance and the temperature and the material and the property change:
S o
g
where k is the reaction rate constant of the process
EA A is an Arrhenius pre-exponential factor
n

i
EA is the apparent activation energy (in J.mol-1)

k  AE e
t
R is the gas constant (8.314 J.mol-1·K-1)
RT T is the absolute temperature (in K)
s
α is a material specific coefficient
e
E is the effective irradiance (in W·m-2)
T
@ T~25°C 3 5 7 10 12 15 Ea (kCal/mol)
l
Delta T (°C) 13 21 29 42 50 63 Ea (kJ/mol)
i a
5 6% 15% 22% 32% 40% 52%
r
10 12% 32% 47% 73% 93% 128%
t e
20 24% 70% 110% 189% 258% 392%
a
30 36% 116% 195% 369% 538% 914%
40 49% 172% 305% 638% 1000% 1904%
M Range of polyolefins
s
Range of discoloration and gloss loss for
photooxidation
a
coatings and engineering polymers
t l
Approximation rule: A 10 °C temperature increase will double the overall
A
degradation rate  Most often disobeyed!!!
s
Example: Temperature Effects
o n
Ranking effects:
t i
lu
Fluorescent UV lamp, 45W/m² (300-400 nm)
S o
n g
i
Polyamide
t
Polyester
Residual strength, in %
Residual strength, in %
s
Polypropylene
e
Polyamide
T
Polyester
l
Polypropylene
r i a
t e
a
Duration of weathering (in weeks) Duration of weathering (in weeks)
M
Acc. to TABOR and WAGENMAKERS
a s
l
Conclusion: Acceleration by temperature increase is material dependent!
A t
s
Temperature Effects: Tg of Polymers
o n
The Glass Transition Temperature (Tg) is the temperature where a polymer changes
t i
u
from a hard, vitreous or “glassy” state to a flexible “rubbery” state.
o l
S
n g
t i
e s
l T
r i a
t e
a
http://www.epotek.com/site/files/Techtips/pdfs/tip23.pdf
M
s
• Chemical and physical properties are different below and above T g
la
(like thermal expansion)
t
• Above T photooxidation is accelerated due to increased O diffusion
A
g 2
through the enlarged and more flexible polymer structure
s
Lessons learned “the hard way”
o n
i
• Perception:
u t
l
- A more severe (harsher – “big hammer”) test will just accelerate the rate of
o
natural weathering degradation. “We won’t pass any bad material”.
• Reality
S
n g
i
- Can alter the degradation mechanism (chemistry) sometimes resulting in
t
less or different degradation.
e s
- A “different” test than real environment may produce a “different” result.
T
This may be less severe than the actual weathering.
l
- A more severe test may require “over-Engineering,” significantly increasing
a
i
material cost by adding non-essential stabilization.
er
at
M
a s
t l
A
ns
t i o
lu
So
n g
t i
e s
Correlation and
l T Correlation
r i a
Factors
t e
a
M
a s
t l
A
s
Correlation
Correlation in weathering addresses the relationship between two tests,n
t i o
u
based on specific material characteristics and property change.
a)
o l
Artificial weathering (reduced test time/accelerated) versus outdoor weathering
S
n g
t i
e s
l T
i a
b) Different instrument types
e r
a t
M
a s
t l
A
s
Correlation vs. Relevance
o n
Correlation - Quantitative
t i
l u
- The mathematical relationship between weathering results
o
achieved with two different tests
- Usually measured using macroscopic properties
S Rank,
n g
- Determined with statistical methods (e.g., Spearman
Pearsons’ Correlation Coefficient)
t i
Relevance - Qualitative e
s
l T
a
- Same chemical degradation pathway as in “real life“
r i
- Determined by e
- Measured using microscopic / molecular / chemical properties
a t using analytical methods
M
a sRemember: Correlation ≠ Causation
t l
A
s
Correlation - Acceleration
Factors that may decrease correlation (ISO 4892-1 and ASTMn
t i o
u
G151):
o l
S
• Short wavelength exposure
• Spectral distribution with high deviation fromg
n
sun radiation
t i
• High intensity exposure
e s
• Continuous exposure to light
l T
r i a
• Unrealistic specimen temperatures
• Water quality used e

a t
M
• … and others
a s
t l
A
s
Description of Correlation
o n
Examples:
t i
lu
o
• General: Ranking
S
• Better: Statistics
n g
t i
To describe correlation statistics are used,
s
especially the determination of coefficients according to
e
 Spearman (r ) - RankTcorrelation coefficient
s
a l
r i
t e
a
M (r ) - Correlation coefficient
 Pearson
s
p
t la
A
s
Correlation Coefficients
o n
Pearson (rp)
t i
lu
o
Application for measured values which are nearly
normally distributed S
The coefficient values lie between n –1g
t i and +1
e s
The higher the correlation coefficient
l T
(closer to +1), the better the relationship between the
variables
r i a
r e
n(XY )  (X )(Y )
Formula: tp 
a [nX  (X ) ][nY  (Y ) ]
2 2 2 2
M
a s
t l Note: Formula included in MS Excel program
A
s
Pearson’s Correlation Coefficient
o n
B
t i
u
C
o l
A
S
g
Gloss
t i n
e s
l T
Radiant Exposure
Evaluation methods:
r i a
 Radiant exposuree
A – Specified degree of property
t
change
aexposure (or test duration)

values (or test duration)
Mproperty change
B – Specified radiant
s
 degree of
a
t l max. Std. deviation)  Degree of property change
C – Radiant exposure at highest property difference
A
(e.g.
s
o n
t i
u
Evaluation of rp – Example: Method A
o l
S
n g
t i
e s
l T
i a
Test 1 Test 2
er
at
M rp = 0.0871
a s for only 3
t l materials!
A
Pearson’s Correlation
ns
t i o
lu
Correlation Coefficient = 1.0 Correlation Coefficient = 0.98 Correlation Coefficient = 0.9
o
(perfect correlation) (excellent correlation) (very good correlation)
S
Outdoor Weathering Result
n g
t i
e s
Accelerated Weathering Result
l T
Accelerated Weathering Result Accelerated Weathering Result
r i a
Outdoor Weathering Result
t e
a
M
a s
l
Accelerated Weathering Result Accelerated Weathering Result Accelerated Weathering Result
t
Correlation Coefficient = 0.7 Correlation Coefficient = 0.3 Correlation Coefficient = 0.0
A
(good correlation) (poor correlation) (no correlation)
according to L. Scott Crump, SPI Reprint, 1996
s
o n
Calculation with Excel:
t i
Function in MS Excel
lu
2 data sets – Florida and instrument
o
Same irradiance
S
Automotive
textiles
Criteria:
n g
i
color change E*
st
Te
a l
r i
t e
a
M
a s
t l
A
s
Cautions with Pearson Coefficients
o n
t i
lu
S o
n g
t i All data sets:
e s rp = 0.816
l T
r i a
t e
a
M
s
Pearson correlation works best with normally distributed data sets:
t la
- similar materials
- similar sensitivity to the stress factors
Anscombe, Francis J. (1973)
Graphs in statistical analysis.
A- no extremely sensitive or un-sensitive materials American Statistician, 27, 17–21.
s
Example: Correlation Study – Gel Coats
o n
Gel-Coat Composite Material
t i
lu
So
Test Objectives
n g
t i
Find best correlation and acceleration
e s
T
Lower test costs - eliminate poor methods
l
i a
Determine validity of competitive claims
r
t e
L.Scott Crump, Director Corporate R&D
a
M
Cook Composites and Polymers
a s
t l
A
s
o n
i
Materials tested
- Ten different formulations of gel coats
u t
o l
S
- Each formulation had different stabilities
- Three colors (red, white and blue) wereg

coat grade
t i n tested for each gel
- .
e s
l
were tested in each method. T
- In total, 30 different specimens (10 formulations x 3 colors)
ia to increase confidence level

- Several replicatesrtested
t e
- Gloss anda
M to 3 month intervals outdoors)
color data taken at several intervals (approx.
s
corresponding
-la
A t Outdoor Miami 45-degree exposures were the benchmark;
evaluations were CIE L*a*b* color and gloss loss
s
o n
t i
FEATURES OF WEATHERING DEVICE l
u
S o
g
(ENVIRONMENTAL STRESSORS)
t i n
s
Method Light Source Moisture Max Temp
UVB-313 Bulbs Unrealistic
T e cond. cycle 60° C
UVA-340 Bulbs
a l
UV component only cond. cycle 60° C
Carbon Arc
r i (good match) none
UV/VIS (poor match) water spray 63° C
Small Xenon
t e (good match) water spray 70° C
UV/VIS 44° C
Large Xenon
a Magnified sunlight water spray ----
UV/VIS
M
Solar Concentrator
a s
t l
A
s
o n
t i
lu
So
n g
t i
e s
l T
r i a
t e
a
M
a s
t l
A
s
Correlation - Ranking
o n
Coatings A - D; Color change ΔE* after 1 year Florida and
t i
artificial weathering in time intervals [hours]
lu
(part of a VDA-Round robin, ISO 11341/ISO 16474-2)
S o
n g
18,0 18,0
i
A
t
16,0 16,0 A
s
B
14,0 14,0 B
e
C
12,0 C
T
12,0
D
Delta E*
l
10,0 D
Delta E*
10,0
i a
8,0 8,0
r
6,0 6,0
t e
4,0 4,0
a
2,0 2,0
M
0,0
0,0
0 500 1000 1500 2000 2500 3000
s
Gerät 2000 h
Instrument Florida 1 Jahr
Florida Gerät 2320 h
Instrument
Accel. Weathering (Hours) (extrap.)
a
2000 hours 1 year 2320 hours
t l
A
Same ranking after 2320 h Xenon weathering as after 1 year Florida.
s
Spearman’s Rank Correlation
6  Dio
n
t
2
rs = 1
l u
n(n 2
-1)
o
Formula: Spearman ( rs )
S
Different materials with different ageing behaviour
g
here: Example (Coatings A to F) n = number of pairs
n
D = difference in rank
i
Measuring values (dataset e.g. loss of gloss)
t
from outdoor weathering - e.g.
s
Florida 1 year or 180 MJ/m²
Values from Instrumental

Te
exposure as function of time
a l
r i
e
Florida 1 year
Instrument 400 h
at
M
a s
t l
A
s
Ranking: Example
o n
t i
lu
6 polymer materials; gloss loss (relative) after one year Florida resp. 400
hours of artificial exposure.
S o
g
Determination of ranking (1 to 6)
Materials Florida 1 year
t i n
Device Exposure 400 h
Difference D D2
s
n=6 Gloss 20° Ranking Gloss 20° Ranking
e
A 84 3 97 1 -2 4
B 78
l
5
T 90 2 -3 9
a
C 81 4 85 3 -1 1
D 96
r i 1 80 5 4 16
t e
E 89 2 66 6 4 16
a
F 68 6 82 4 -2 4
M
SUM D2 = 50
s 6D 2
a n(n -1) = 1 – 300/210 = - 0.43

r =1
l
s 2
A t
s
Spearman: Optimum Time for Comparison
o n
t i
u
Florida 1 year
o l
Instrument 1000 h
S
n g
t i
e s
l T Optimum Time for
a
Comparison
r i
t e
a
M
a s
t l
A
Florida 1 year Time [h]
www.atlas-mts.com
Instrument 400 h 59
s
Example: Ultra-durable Powder Coatings
o n
Correlation depends on the approach:
t i
lu
S o
Easy Approach
g
All FL samples pass the
i n
test (50% residual gloss)
t
 good correlation (?)
50 %
e s
l T
r i a
t e
a
M
M. Witter, C. Dreyer, European Technical Coatings Congress 2012
Better: Statistics
s
3 years Florida 15 10 5 14 4 13 6 12 11 8 1 7 3 9 2 e.g.. Spearman
a
8 10 2 12 15 16 14 1 9 3 4 13 5 6 11 7
l
600 h UVB
t
D 7 0 3 2 -11 -1 5 3 8 4 -12 2 -3 -2 -5 rs = 0.136
A
D2 49 0 9 4 121 1 25 9 64 16 144 4 9 4 25
 very poor correlation
Testing Considerations
ns
t i o
u
• Number of available data sets (helps to determine which
statistic to use for data analysis)
o l
• Distribution of data S
n g
i
• Number of replicates
st
• Choosing the right test method/conditions
Te
• Understanding Measurement Technique (precision,
a l
reproducibility, sensitivity, change effect)
r i
• Balancing acceleration with correlation
t e
a
• Test to failure, to a specified Δ in property or to a specified
M
radiant exposure (better than time)
s
• Choosing the correct exposure/measurement interval
a
t l
A
s
Summary: Correlation and Acceleration
o n
• A compromise must be made between correlation and
t i
acceleration
lu
o
• “The faster the test, the more likely it will not correlate”
S
g
• Acceleration factors of 10 or higher are extremely
material/environment specific
t i n
• There is no universal acceleration
e s factor
T
• There is no universal correlation factor
• Correlation factors are lbest done empirically using
r i a
e
well-knows statistical methods and only after materials
have shown some
• Two tests a t don’t cause change to a set of materials
that
amount of degradation
M
DOES NOT mean the two tests correlate
a
• Twos tests that completely fail materials before they are ever
t l evaluated DOES NOT mean the two tests correlate
A
s
Upcoming Events
o n
Tuesday
t
Wednesday
i
u
Online Seminar Schedule (UTC)
l
06:00-07:00 13:00-14:00
o
More online Seminars starting coming in August/September 2017
Live Seminar Schedule

S
g
Date Location Country Language
n
The Fundamentals of Weathering I + II June 19/20, 2017 Tel Aviv Israel EN
t i
The Fundamentals of Weathering I + II June 27/28, 2017 Freiburg Germany DE
s
Ci Weather-Ometer Workshop July 18, 2017 Mount Prospect USA (Illinois) EN
e
The Fundamentals of Weathering – the Basics July 19, 2017 Mount Prospect USA (Illinois) EN
T
Bangalore,
l
Technical Seminars – Textile, Automotive, Plastics July 24 -28, 2017 Coimbatore, New India EN
a
Delhi, Pune
r i
More events 2017: Sanary-sur-Mer (France), Kassel (Germany), Linsengericht (Germany), Mount Prospect (USA),…
Trade Shows
t e
a
Title Location Booth
June 28, 2017 - June 30, 2017 Japan Automotive Engineering Exposition 2017 Nagoya, Japan
M
September 13 - 15, 2017 - Asia Pacific Coatings Show 2017 Jakarta, Indonesia D19
s
September 19 - 21, 2017 Automotive Test Expo China 2017 Shanghai, China 6000
t la
October 16 - 19, 2017 testXpo Ulm, Germany
A For registration or more information please visit http://atlasmtt.com/onlinefow

s
Questions and Answers
o n
t i
u
Thank You!
o l
S
n g
t i
e s
l T
r i a
t e
Atlas Material Testing Technology Atlas Material Testing Technology GmbH
1500 Bishop Court
a Vogelsbergstraße 22
M
Mount Prospect, Illinois 60056, USA 63589 Linsengericht, GERMANY
s
Phone +1-773-327-4520 Phone +49-6051-707140
la
Fax +1-773-327-5787 Fax +49-6051-707149
A t E-Mail atlas.info@ametek.com

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ns

t l Atlas Online Seminar

a s over 250 career long educational technical seminars

a l • Not an ISO, ASTM, etc. standard

t e How long should I test to achieve the

T e > Natural max

t l - vs. Central Europe: 20X !!!

A test conditions and the material!

A t Uncommon: increased irradiance + increased temperatures

Radiant exposure: H (300-400 nm) = 13,200 kJ/m²

ΔOD at 1780 cm-1

ΔOD at 1780 cm-1

ΔOD at 1780 cm-1

ΔOD at 1780 cm-1

 HarshsUVB-313 test leads to reversal of ranking

The modified Arrhenius equation describes the influence of temperaturen

S oSchematic diagram of the potential

Relative Potential Energy

st Low Ea, little temperature effect

Note:ainsweathering often a 20-30% increase of the reaction

t lis observed by a 10K increase

a t using analytical methods

• Water quality used e

aexposure (or test duration)

A- no extremely sensitive or un-sensitive materials American Statistician, 27, 17–21.

- Three colors (red, white and blue) wereg

ia to increase confidence level

Values from Instrumental

a n(n -1) = 1 – 300/210 = - 0.43

t l evaluated DOES NOT mean the two tests correlate

Live Seminar Schedule

A For registration or more information please visit http://atlasmtt.com/onlinefow

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