140225 Composites EXPO 2014

DOW EPOXY BUILDING BLOCKS
=
UNLIMITED POSSIBILITIES FOR THE COMPOSITE INDUSTRY
THE DOW CHEMICAL COMPANY IS A GLOBALLY LEADING SUPPLIER OF
INDUSTRIAL RAW MATERIALS FOR MANY APPLICATIONS. OVER THE LAST
DECADES DOW HAS ESTABLISHED ITSELF AS A MAJOR GLOBAL PRODUCER
TOF HIGH QUALITY EPOXY PRODUCTS. THE CHEMISTRY OF SOME BUILDING
BLOCKS WILL BE EXPLAINED AND THEIR RELATION TOWARDS PRODUCT
PROPERTIES SUCH AS MECHANICAL STRENGTH AND TEMPERATURE
RESISTANCE (E.G. GLASS-TRANSITION TEMPERATURE)..
Composite-Expo - 2014
7th International Specialized Exhibition
on composite materials and technologies
Moscow, RussiaToine Dinnissen, February 25th 2014

Outline
The Dow Chemical CompanyThe Dow Chemical Company
• Epoxy business & Commitment,
Epoxy Compositespo y Co pos es
• Bisphenol-A Epoxy Resins
• Curing Agents
l P t lif / hi h fl ibilit– long Pot-life / high flexibility
– high temperature resistance
• Bisphenol-F Epoxy Resin
• Epoxy Novolac Resins
• Curing
– Gelation– Gelation
– Crosslink Density
– Glass Transition
Toine Dinnissen, February 25th 2014
• New development Novolac

The Dow Chemical Company
• Founded in 1897 by Herbert H. Dow in Midland, Michigan
• Supplies broad range of products / services in about 160 countries
• More than 5,000 products manufactured at 188 sites in 35 countries
• Employs 52,000 employees worldwide
A l l f $57 billi (2013 +1%)• Annual sales of $57 billion (2013 = +1%)
• $1.7B in R&D investment (2012)
Our Mission
To passionately innovate what is essential to human progress by providing sustainable
solutions to our customers
2010 – Dow becomes a
Worldwide Partner and the
“Official Chemistry Company”
of the Olympic Games
of the Olympic Games

Dow Epoxy
•The world’s largest producer of epoxy resins & intermediates.
• Broad product mix & strong global presence.
• Eight manufacturing facilities in:Eight manufacturing facilities in:
• Asia Pacific – China, Korea
• Europe – Germany, Italy
• Latin America – BrazilLatin America Brazil
• North America – USA
• Backward integration into feed-stocks that allows consistent,
reliable product supplyreliable product supply.
• Almost 60 years of industry service
• Strong commitment to product technology & solution innovation
Strong re investment in the business• Strong re-investment in the business
• Continuously improving our business to:
• maintain reliable partner for our clients
• create shareholder value
• create shareholder value

Epoxy Products in Composites
Features:
• Excellent adhesion to many (difficult) substrates
• Low shrinkage upon cure
• Excellent Chemical Resistance
• Excellent Mechanical Properties
• Good Heat ResistanceGood Heat Resistance
• …
Often used to produce light weight composite parts that can replace metal articles.
e g FRP pipes automotive parts storage tanks wind mill bladese.g. FRP pipes, automotive parts, storage tanks, wind-mill blades, ….
™ Trademark of The Dow Chemical Company

Mechanical Properties Comparison
Black Steel Stainless Steel Hastelloy® C GRPBlack Steel Stainless Steel
316
Hastelloy® C GRP
(Mat & Roving)
Density [gr/cm3] 7.8 7.9 8.9 1.5
Tensile Modulus [GPa] 207 193 180 10 15Tensile Modulus [GPa] 207 193 180 10-15
Tensile Strength [MPa] 450 590 550 120-250
Heat Conductivity [W/mºC] 46 15 12 0.2
Thermal Expansion
Coefficient
[mm/mm ºC]x10-6
12 16 12 23
PE PP PVC PVDF GRP
Density [gr/cm3] 0.95 0.90 1.4 1.75 1.5
Tensile Modulus [MPa] 80 80-130 300-350 1200 10 000-15 000Tensile Modulus [MPa] 80 80 130 300 350 1200 10,000 15,000
Tensile Strength [MPa] 30 30 60 50 120-250
Heat Distortion 40 45 75-100 90 100-200
Temperature [ºC]
All data are typical data and not to be construed as specifications

Fibre Reinforced Composites
Property Epoxy Unsaturated Polyester (UPR) and
Epoxy Vinyl Ester Resin (EVER)
Phenolic
Cure mechanism Polymerization of resin
plus hardener
Catalytic
copolymerization
Condensation
Polymerizationplus hardener copolymerization Polymerization
(produces water)
Wet impregnation, typical
system
Liquid resins plus amine
or other hardeners
Styrene-modified resins plus peroxide
catalysts
Liquid phenolics plus acid
catalysts
Cure temperature (°C) 25 150 25 100 25 170Cure temperature (°C) 25-150 25-100 25-170
Typical cure time (min) 60-180 10-60 60-180
Stability of resin (alone) Excellent Fair Poor
Cure shrinkage of system Low (2 3%) High (6 8%) HighCure-shrinkage of system Low (2-3%) High (6-8%) High
Adhesion to metal Excellent Fair Fair
Physical properties of
cured laminate
Excellent Excellent Excellent/Bad (best heat
resistance, most brittle), )
All data are typical data
All data are typical data
and not to be construed
as specifications

Epoxy Resin Route
Crude Oil Brine Salt
Naphta Electrolysis
Benzene Propylene CL2 NaOH
Cumene Allylchloride
OH O
OOH
HOCl
Ca(OH)2
Cl
Acetone Phenol
EpichlorohydrinBisphenol-A
OH O
OHHO Cl
O
Polycarbonate Epoxy Resins

Standard Bisphenol-A epoxy resin
Bisphenol A
O
Cl
Epichlorohydrin
O
Cl
OHHO
Bisphenol A
(A = Acetone)
Epichlorohydrin Epichlorohydrin
OO
O O
DGEBA = Diglycidylether of Bisphenol A
BADGE = Bisphenol-A Diglycidylether
LER = standard liquid epoxy resin
D.E.R.™ 33X-series
Viscosity = ± 4000 mPa.s
Toine Dinnissen, February 25th 2014 ™ Trademark of The Dow Chemical Company

Higher Molecular Weight Species
Cl
O
+
OHHO
Resin n=0
NaOH
OO
O O
Diglycidyl ether of bisphenol A (DGEBA)
NaOH
NaOH
OO
OH
O
OO
O
n
Diglycidyl ether of bisphenol A - Oligomer n=1,2,3...
Typically between 5 and 15%Increase in viscosity

Mono-Hydrolyzed Resin (alpha-glycol)
OO
O O
O OH
Cl
O
H2O
Diglycidyl ether of bisphenol A (DGEBA) OH
1,2-Diol / α-Glycol
Monohydrolyzed Resin (MHR)
function
Typically between 0.1 and 5%
OO
OH
OH
O
Increase in viscosity
Increase in OH groups – can have impact on wetting, adhesion and reactivity
D i E F ti lit
Decrease in Epoxy Functionality

Bisphenol-A Liquid Epoxy Resins
D.E.R.™ 332
Epoxy Resin
D.E.R. 330
Epoxy Resin
D.E.R. 331™
Epoxy Resin
Epoxide Equivalent Weight [gr/eq]
A S T M D 1652
171 – 175 176 ‐ 185 182 – 192
A.S.T.M. D‐1652
Viscosity @ 25 °C [mPa.s]
A.S.T.M. D‐445
4000 – 6000 7000 ‐ 10000 11000 ‐ 14000
340 / average EEW 1 97 1 89 1 82340 / average EEW 1.97 1.89 1.82
Mix with D.E.H.™ 24 hardener [phr] 14.0 13.5 13.0
Mix‐viscosity @ 25 °C [mPa.s] 900 1250 2250
Time to gel, 500 grams [min] 43 40 25
Heat Deflection Temperature [°C] 107 104 111
with Nadic‐Methyl‐Anhydride [°C] 156
with BF3‐MEA [°C] 168

Bisphenol-A Liquid Epoxy Resins
Resin D.E.R.™ 330 Epoxy Resin D.E.R. 331™ Epoxy Resin
D.E.H.™ 24 Hardener wt% Change wt% Change
Days; 7 28 120 7 28 120Days; 7 28 120 7 28 120
Sulphuric Acid (30%) 0.56 1.24 2.85 0.69 1.80 3.10
Acetone 0.17 0.74 4.48 0.45 2.10 7.70
Sodium Hydroxide (50%) 0.00 ‐0.06 ‐0.11 0.00 0.04 0.02
Jet‐fuel 0.03 ‐0.01 0.09 0.02 ‐0,01 0.09
Distilled Water 0.40 0.79 1.68 0.41 0.88 1.70
Thermal Degradation
Hours 100 200 300 500 100 200 300 500
eight loss @ 160 °C 0 95 0 95 1 32 1 41 0 71 1 00 1 40 1 60weight loss @ 160 °C 0.95 0.95 1.32 1.41 0.71 1.00 1.40 1.60
weight loss @ 210 °C 2.11 3.77 7.39 3.40 5.40 6.80 7.80

Recent Innovation More FlexibilityRecent Innovation – More Flexibility Color 30 APHA
Amine number 472 mg KOH/g
Viscosity 15 mPa.s @ 25 °C
Density 0.96 g/cm3
Mol. Weight 230
AHEW 63 gr/eq
D.E.R.™ 330 epoxy resin 100 100
D.E.H.™ 23 amine hardener 32 25
IPDA ‐ 5
Mix‐viscosity [mPa.s @ 23°C] 320 620
Tg [°C]; DSC 90 98
D.E.H. 23
80
90
100
Flexural Strength [MPa] 102 131
Flexural Modulus [GPa] 3.14 3.38
Tensile Strength [MPa] 66 9 73 8
50
60
70
80Tensile Strength [MPa] 66.9 73.8
Izod impact Strength [cm‐kg/cm] 7.08 8.17
Elongation at Break [%] 10.0 8.0
20
30
40
20 2 28 32 36 0
Glass Transition Temperature [°C]
Heat Deflection Temperature [°C]
20 24 28 32 36 40 44
Theoretical mixing Ratio : 31.1 phr D.E.R. 330 epoxy resin
Empirical mixing ratio : 32.0 phr D.E.R. 330 epoxy resin

Glass Transition Temperature, Tg
Tg = The Temperature Range where a polymer changesTg = The Temperature Range where a polymer changesg p g p y g
from Glass to Rubber
* Secondary Bonds are Broken
* Molecular Mobility Increases
g p g p y g
from Glass to Rubber
* Secondary Bonds are Broken
* Molecular Mobility Increasesy
* Free Volume Increases
* Strength Decreases
* Flexibility Increases
* Internal Stress is Relieved
y
* Free Volume Increases
* Strength Decreases
* Flexibility Increases
* Internal Stress is Relieved
25
30
Slow Cure
Cure is diffusion controlled
Glassy
15
20
VitrificationFast Cure
Tg = Cure Temp.
Liquid /Rubber
5
10
When the Tg of the Growing Polymer Reaches the Cure
Temperature, The Polymer Vitrifies
Extend of cure is determined by the Tg, Average Functionality
Liquid /Rubber
Cure is
Kinetically
C t ll d
0
0 2 4 6 8 1 0 1 2 1 4
Cure Time
te d o cu e s dete ed by t e g, e age u ct o a ty
Controlled

Recent Innovation High TemperatureRecent Innovation – High Temperature
4,4'-Methylenedianiline (MDA) is a suspected
carcinogen. It is included in the "substances of very
high concern" list of the European Chemicals Agency
(ECHA)
DiethyleneTolueneDiamine
(ECHA).
Pure methylenedianiline is a highly toxic, colorless solid.
May be fatal if swallowed, inhaled or absorbed
through skin. Causes irritation to the skin, eyes and
respiratory tract. Combustible solid or liquid when heated.p y q
May cause methemoglobinemia. Affects blood,
cardiovascular system, central nervous system, liver and
kidneys and may cause cancer.
Ancamine DL-50 (MDA-blend)
Highly viscous / solid = light to dark brown @ 50,000 - 55,000 mPa.s (AHEW = 51 gr/eq)
DETDA
Low viscosity liquid = clear amber liquid @ 100 200 mPa s (AHEW = 46 gr/eq)
Low viscosity liquid = clear amber liquid @ 100 - 200 mPa.s (AHEW = 46 gr/eq)
Need 10% less per 100 kilo epoxy
Much lower viscosity = allows blending and use at much lowers
temperatures (room temperature)

D.E.H.™ 650 Curing Agent

R t I ti Hi h T tL b li di EC Di i Recent Innovation – Higher TemperatureLabeling according to EC Directives:
Hazard Symbol: Xn ‐ Harmful
N ‐ Dangerous to the Environment
Risk Phrases: R 21/22 ‐ Harmful in contact with skin and if swallowed.
R 48/22 ‐ Harmful: danger of serious damage to health by prolonged exposure if swallowed
R 36 ‐ Irritating to eyes
ASTM D‐790
3 point Flex
MDA Ref. D.E.H.™ 650
R 36 Irritating to eyes.
R 50/5 ‐ very toxic to aquatic organisms, may cause long‐term adverse effect in aquatic environment
D E H ™ 650 hardener @ 37 °Cp
Tg (DSC, °C) 167 178
Flexural Strength
[MPa]
110 116
D.E.H. 650 hardener @ 37 C
Modulus [MPa] 2707 3137
Strain [%] 8.3 6.3
Stress @ Break
[MPa]
106 116
[MPa]
K1c Fracture
Toughness
0.76 0.61
MDA-reference @ 57 °C
Pot-life 150 grams

Bisphenol-F Epoxy Resins
OH OH
O
Cl
O
O
O
O
Bisphenol F
(F = Formaldehyde)
Epichlorohydrin
Diglycidylether of Bisphenol-F
O
OO
OO
O
O
O
O
O
O
para - para
O
O
O
O
O
O
n
O
O
ortho - para
ortho - ortho
D.E.R.™ 354 liquid epoxy resin

Epoxy Novolac Resins
OH OHOH
O
O O
O O
O
O
Cl
+
n
n
Phenol Novolac Epichlorohydrin Epoxy Novolac Resin
n = 0 - 0.2 for D.E.R.™ 354 liquid bisphenol-F epoxy resin
n = 0.4 for D.E.N.™ 425 LIQUID epoxy novolac resin
n = 0 8 for D E N 431 epoxy novolac resinn = 0.8 for D.E.N. 431 epoxy novolac resin
n = 1.6 for D.E.N. 438™ epoxy novolac resin
n= 1.8 for D.E.N. 439 epoxy novolac resin
Higher epoxy functionality ===> Higher crosslink density
Excellent solvent/chemical resistance.
Higher Temperature Resistance
Gel at lower conversion
Gel at lower conversion

MTHPA versus DETDA
D E H ™ 70 [MTHPA] D E H 650 [DETDA]D.E.H. 70 [MTHPA] D.E.H. 650 [DETDA]
Resin D.E.R.™ 330 D.E.N.™ 438™ D.E.R.™ 330 D.E.N.™ 438™
EEW [gr/eq] 176 – 185 176 - 181 176 – 185 176 - 181
Mix-ratio [phr] D.E.H. 70 / MI
85 / 1
D.E.H. 70 / MI
85 / 1
26.0 26.3
Cure Schedule; Hours @ °C 2 hrs @ 85 °C
3 hrs @ 150 °C
2 hrs @ 85 °C
2 hrs @ 150°C
2 hrs @ 200 °C
2 hrs @ 120 °C
2 hrs @ 177 °C
2 hrs @ 120 °C
2 hrs @ 177°C
2 hrs @ 225 °C2 hrs @ 200 C 2 hrs @ 225 C
Glass Transition Temperature [°C] 148 149 182 220
Coefficient of Linear Expansion [ppm/°C] 70 66 74 69
%Water Absorption, 2 weeks boil [%] 1.45 1.49 2.35 2.47
Flexural Strength [MPa] 128 138 108 110
Flexural Modulus [GPa] 3.27 3.51 2.64 3.06
Strain @ Yield [%] 6.7 6.7 6.9 6.1
Cured density [gr/cm3] 1.190 1.224 1.140 1.210

Gelation versus Functionality
Active Groups per Molecule 2 Functional Epoxy Groups
OO
OH
O
OO
O
n
5 Functional Amine-Hydrogen Groups
Functionality ≤ 2 Linear Molecular Weight BuildFunctionality ≤ 2 Linear Molecular Weight Build
A A B B A A B B
A
B
No Cross linking
Functionality > 2 Cross Linking
Functionality > 2 Cross Linking
Cross linking leads to gelation

Gelation
∞
Covalently Bonded Polymer Network
Molecular Weight Infinitely High∞Molecular Weight Infinitely High
Gel = “One” macromolecule
S l L l l i h f i
Polymer Properties develop at Gel-Point
Sol = Low molecular weight fraction
y p p
Solvent Soluble Solvent In-soluble
Sol Gel
M No Physical Strength
Fluid Behavior
50% of Shrinkage
Physical Strength
Elastic Behavior
50% of Shrinkage
Gel Point
Monomers

Gel-point can be Predicted
/Carothers: % Cure @ Gel Ξ 2 / favg
Flory: % Cure @ Gel Ξ 1
[1 + (f-2)]1/2
Gelation is Controlled by Functionality
[1 + (f-2)]
react 3 moles of D E R ™330 epoxy resin = 6 reactive groupsreact 3 moles of D.E.R. 330 epoxy resin = 6 reactive groups
with 2 moles of amino-ethyl piperazine = 6 reactive groups
average functionality = 12 groups / 5 mole = 2.4
Gel Point ~ 2/2.4 ~ 83% cure at Gel
react 7 moles of D E R ™330 epoxy resin = 14 reactive groupsreact 7 moles of D.E.R.™330 epoxy resin = 14 reactive groups
with 2 moles of tetra-ethylene-pentamine = 14 reactive groups
react 14 moles of D.E.N.™425 epoxy resin = 35 reactive groups
with 5 moles of tetra-ethylene-pentamine = 35 reactive groups
Gel Point 2/3.68 54% cure at Gel
Higher Functionality is Early Mould Release

Crosslink Density:
High Crosslink DensityHigh Crosslink DensityHigh Crosslink DensityHigh Crosslink Density
High Chemical & Heat Resistance
Strong, Rigid
Heat Cure Needed
D.E.N.™438™
D.E.R.™324
Low Crosslink DensityLow Crosslink Density
Moderate Chemical & Heat Resistance
Flexible ToughFlexible, Tough
Cure at Lower Temperatures
Fl l St th 21 000 iHigh X-Link Density
D.E.R.™ 331 / Imicure(1) EMI 24
Cure @ 150 °C
Flexural Strength 21,000 psi
Flexural Modulus 540,000 psi
Elongation @ Break 2 %
Glass Transition 160 °C
3 h t b il 1 % t i
Low X-Link Density
D.E.R.™ 331 / Jeffamine(2) D-400
C @ 30 °C
3 hr acetone boil 1 %wt gain
Flexural Strength 11,200 psi
Flexural Modulus 406,000 psi
Cure @ 30 °C Elongation @ Break 60 %
Glass Transition 30 °C
3 hr acetone boil 29 %wt gain

Tg versus Cured Property
Tg < Service TemperatureTg > Service Temperature
Epoxy Cycloaliphatic Amine Epo Pol amideEpoxy-Cycloaliphatic Amine
Cured @ 100°C
Tg = 110°C
Service Temperature 80°C
Epoxy-Polyamide
Cured @ 25°C
Tg = 30°C
Service Temperature 40°C
Glassy, Rigid
Low Impact Resistance
High Internal Stress
Higher Barrier Properties
Rubbery, Tough
High Impact Resistance
Low Internal Stress
Lower Barrier Properties
Functionality TgGel PointCrosslinking
Gel Point
Dry Time
Pot Life
Chemical
Resistance
Strength
Rheology
Chemical
Resistance
Shrinkage
% Cure
Glass/Rubber
Internal Stress
Shrinkage
Reactivity

D.E.N.™ 440 High Functionality
Epoxy Novolac Resin
Part A
D.E.N.™ 438™ epoxy
novolac
D.E.N. 440 epoxy
novolac
Epoxy Resin 80.2 80.2
Part B
D.E.N.™ 425 (f=2.5)
Part B
D.E.N. 431 19.8 19.8
DICY 5.6 5.6
UREA 2 8 2 8
D.E.N. 431 (f=2.8)
D.E.N. 438™ (f=3.6)
UREA 2.8 2.8
Uncured rheology
properties
D.E.N. 439 (f=3.8)
D.E.N. 440 (f=4.5 !!!)
η* @ 80oC (Pa*s) 1.5 6.4
G* @ 1rad/s
(MPa@25°C))
0.005 0.21
Cured polymer
tiproperties
Tonset (oC) 117 117
Tg (oC)160oC cured 193 215
Flexure Modulus (GPa) *2 93 *3 53
Flexure Modulus (GPa) 2.93 3.53
KIC (MPa*m0.5) *0.58 *0.52

Summary
The Dow Chemical Company Epoxy business is Committed and Reliable partners for our Clients
• High Quality standard Raw Materials
• D E R™ 33x epoxy resins• D.E.R 33x epoxy resins
• D.E.N.™ 43x epoxy novolac resins
• D.E.H.™ curing agents (incl. D.E.H. 70 anhydride hardener)
• Higher Temperature Performanceg p
• D.E.H. 650 curing agent
• D.E.N. 440 epoxy novolac resin
• FORTEGRA™ epoxy toughening technology
• Viscosity
• Diluents (mono-, di- or multi-functional); D.E.R.™ 7xx series
• Bisphenol-F epoxy resin(s); D.E.R. 354, 351, 352
• Cure rate
• Room temperature / Latent master-batch accelerated resins; D.E.R. 34xx
• Long(er) pot-life amine hardeners (D.E.H™ 23 or D.E.H. 2132 curing agent)
Fl ibilit
• Flexibility
• Amines (e.g. D.E.H. 23), diluents (e.g. D.E.R. 732P) or
D.E.R. 3913 Flexible epoxy resins

Контакты
Meet us for face-to-face discussion at the EXPO; Booth G05
Дау Юроп, Московское Представительство
Дмитрий Белобородов
dbeloborodov@dow.com
Dow Europe GmbH
Toine Dinnissen
tdinnissen@dow.com
ЗАО "НЕО Кемикал"
Юлия ТашкиноваЮлия Ташкинова
tashkinova@neochemical.ru
(8313) 32-06-74, 33-68-68, 32-59-63

DOW Epoxy Products
N P d t TName Product Type
D.E.R.™ 31x / 31xx Liquid epoxy resin with non‐reactive diluents / additives
D.E.R. 32x / 32xx Liquid epoxy resin with reactive diluent(s)
D.E.R. 33x / 33xx Unmodified bisphenol‐A Epoxy Resin
D.E.R. 34x / 34xx Accelerated liquid epoxy resin
D.E.R. 35x / 35xx Bisphenol‐F epoxy resin containing liquid epoxy resin, might contain reactiveD.E.R. 35x / 35xx Bisphenol F epoxy resin containing liquid epoxy resin, might contain reactive
diluent (3rd digit can indicate the main reactive diluent type)
D.E.R. 36x / 37x Few “exotic” grades
D.E.R. 38x Only D.E.R. 383 = US version of D.E.R. 330y
D.E.R. 39xx Specialty epoxy resin
D.E.R. 5xx Brominated epoxy resin
D E R 6 S lid iD.E.R. 6xxx Solid epoxy resins
D.E.R. 9xx Emulsions, Dispersions or water‐emulsifiable epoxy resins

DOW Curing Agents
Name Product Type
D.E.H.™ 1xx / 1xxx Polyamide and Amidoamine curing agents
D.E.H. 2x Polyamine building blocksy g
D.E.H. 2xx / 2xxx Modified polyamine(s) / blends
D.E.H. 3x AEP and Accelerators
D E H 4 / 4 F l d E A i ddD.E.H. 4xx / 4xxx Formulated Epoxy – Amine adducts
D.E.H. 5x Simple adduct / blend (her. Dow)
D.E.H. 5xx Formulated Epoxy – Amine adducts; US only (her. GNS)
D.E.H. 6xx Fast & Low temperature curing agents
D.E.H. 7x Anhydride
D.E.H. 8x Phenolic hardeners (powder coatings)D.E.H. 8x Phenolic hardeners (powder coatings)
D.E.H. 8xx Curing agents for aqueous systems.

Recent Innovation - Low Viscosity
Designation Type
D E R ™ 72 f i l i dil
D.E.R.™ 72x mono‐functional reactive diluents
D.E.R. 73x di‐functional reactive diluents
D.E.R. 74x Multi‐functional reactive diluents

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