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13/28/2012
ACRYLIC SHEET
NOUVELLE GENERATION DE PMMA NANOSTRUCTURE :
ALTUGLAS ® SHIELDUP
Jean-Marc BOUTILLIERGroupement de Recherches de Lacq
INNOV ’DAYSLes Plastiques Transparents
Lyon, le 29 Mars 2012
23/28/2012
ACRYLIC SHEET
Vinyl productsIndustrial
ChemicalsPerformance
Products
ARKEMA GROUP
INCUBATOR
The Acrylic BusinessUnit of the Arkema Group
New productsNew technology
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ACRYLIC SHEET
ARKEMA incubator platform : A new business Unit launched in 2008 dedicated to New Products
3 departments :
�Thermoplastic Elastomer�Apolhya
�Supramolecular chemistry�Reverlink ®
400 T plant in 2011
Masterbatches
Electrical dissipation
Flame retardancy
H-bonds cross-links
Polymer-like structure
Self healing
�Carbon NanoTubes�Graphistrength ®
10 nm
�Nanostructured polymers and initiators�Nanostrength ®, BlocBuilder ®, Flexibloc ®
� Based on an Arkema proprietary technology : Controlled Radical Polymerization
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ACRYLIC SHEET
3Businesses :Monomer
PMMA resins
PMMA sheets&blocks
1,300staff
2Research
teams
10manufacturing
sites
650million euros
turnover
2,5%of Turnover
for R&D(corporate)
Altuglas International in brief:
2010
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ACRYLIC SHEET
MEXICO
Production site
Matamoros
Cast sheets
DENMARK
Production site
Bronderslev
Cast sheets & blocks
ITALY
Production sites
Rho
MMA Resins
Porto Marghera
MMA
ASIA
Registered office
Arkema Seoul
Production sites
Jinhae
Resins
Rho
Porto Marghera
MMA
St AvoldBernouville
Bronderslev
Sheets
& blocks
Resins
Jinhae
Seoul
Paris
Headquarters
BristolKensington
King of PrussiaLouisville
Matamoros
Deer Park
USAR&D center
King of Prussia
Production sites
Deer ParkCapacity reservation MMA
LouisvilleResins
Headquarter + Production
site
BristolResins & impact modifiers
Production site
KensingtonExtruded PMMA sheets
FRANCEHeadquarter
La Garenne-Colombes
Production sites
St AvoldCast sheets & blocks
BernouvilleExtruded sheets
R&D Center
Cerdato – Serquign
GRL Lacqy
DENMARKProduction site
BronderslevCast sheets
ITALYProduction sites
RhoMMA Resins
Porto MargheraMMA - base
ASIAHeadquarter
Seoul
Production site
JinhaeResins
MEXICOProduction site
MatamorosCast sheets
R&D
Cerdato
Lacq
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ACRYLIC SHEET
ALTUGLAS INTERNATIONAL
PMMA resinsN°1 in AmericasN°2 in EuropeN°1 in the World for acrylic capstock
Strong, widelyrecognizedbrand names:
PMMA sheetsN°1 in Europe for cast sheets and blocksN°1 brand recognition in Americas
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ACRYLIC SHEET
PMMA : THE organic glass
PMMA is used in different applications thanks to its 4 main key properties : • Aesthetics :
- Transparency :
– Haze < 1%
– Light Transmission : 92% � PMMA is more transparent than glass
- Depth of color - Low optical distortion
• Naturally resistant to UV � the best weathering of all plastics
• High scratch resistance / Surface hardness
• High design flexibility and “Polishable” (to repair surface when damaged)
2 types of transparent PMMA :• Standard PMMA : high rigidity (3300MPa) but brittle
• Impact PMMA : good impact resistance but lower modulus ( � 1700MPa) and becomes hazy when temperature increases
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ACRYLIC SHEET
PMMA : THE organic glass
Typical PMMA applications : • Outdoor : Lighting, Anti noise walls, Skydomes, Car rear lights, Motorbike
windshields, Caravan Windows, Windshield in aerospace, capstock(coextruded sheet ABS/PMMA, PVC/PMMA : Car body panel, …
• Indoor : bathtub, furniture, home appliances , cosmetic, medical,…
However, use of PMMA is limited in demanding applicationslike Automotive glazing for two main reasons :
• Brittle material (use of impact PMMA is not possible)• Limited Chemical resistance to cleaning agents (alcoholbased)
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ACRYLIC SHEET
ALTUGLAS® SHIELDUP : a technical breakthrough
• Based on Arkema proprietary technology, the new PMMA sheet developed and commercialized by Altuglas proposes a real technical breakthrough compared to existing acrylic solutions :
YESYESALTUGLAS®SHIELDUP
NOYESIMPACT PMMA
YESNOSTANDARD PMMA
HAZE NOT SENSITIVE TO
TEMPERATURE
IMPACT
STRENGTH
Very high
Medium
Low
CHEMICAL RESISTANCE
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ACRYLIC SHEET
ALTUGLAS® SHIELDUP sheet : key properties
• The new ALTUGLAS® SHIELDUP sheet offers a new set of key properties :
• High transparency and High impact EVEN AT HIGH TEMP ERATURE
• Unmet Chemical Resistance
• Better Impact / Stiffness balance (compared to current PMMA sheet)
• Very large range of Modulus/ Impact balance achievable (Rigid � Flexible)
• While keeping the key properties of standard PMMA sheet :
• Transparency, optical properties
• UV Resistance
• Scratch Resistance
• “Polishable”
• Lightness
• Easy to thermoform, high design flexibility
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ACRYLIC SHEET
ALTUGLAS® SHIELDUP Cast Sheet : Manufacturing
• The ALTUGLAS® SHIELDUP sheet is manufactured in the Altuglasindustrial facilities by using cast sheet process.
• The high flexibility of the cast process allows Altuglas to propose the sheet in :
• clear or colored or fluo versions
• High gloss or matt surface finish
• large or (very) small quantities
• Broad range of formats :
– Thickness : from 3 to 12 mm
– Size : up to 2.03 x 3.05 m
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ACRYLIC SHEET
Standard high impact cast sheet process
Very few additives : excellent optical properties, better chemical resistance than extruded
But some limitations :• Impact modifier particles content is limited (viscosity) : Standard cast sheets unnotched Charpy
impact = 12 kJ/m², high impact cast sheets = 30 kJ/m²
• Particle size and refraction index mismatch cause haze when T°increases
MAM monomer
PMMA + MAM
Impact resistant cast sheet
Impactmodifier particles
PMMA impact cast sheet
Air oven
t
T°C
Particles ∅∅∅∅ ~ 0.300 µµµµm
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ACRYLIC SHEET
Altuglas ShieldUp cast sheet process: a technical breakthrough
MAM monomer
PMMA + MAM
Technology designed through ARKEMA proprietary Controlled Radical Polymerization process
Flexibloc ® :“Living”
elastomeric polymer
PMMA impact cast sheet
Air oven
t
T°C
No more particlesbut nanostructuration
���� Clarity not T°sensitive
In-situ formation of block copolymer
which acts as veryefficient Impact
Modifier and whichis dispersed at a nanometric scale
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ACRYLIC SHEET
Explanation of the transparency / impact balance and the excellent chemical resistance of Altuglas ShieldUp
new elastomer (acrylic block copolymer) formedduring MMA polymerization, dispersed at a nanometric scale with a « labyrinth » type morphologyto achieve optimal impact and chemical resistances
Elastomeric Core-shell particles (0.3µm) dispersed in the PMMA matrix
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ACRYLIC SHEET
A Non Temperature Sensitive Transparency
3 mm sample
0
5
10
15
20
25
20 30 40 50 60 70 80
Temperature (°C)
Haz
e (%
)
High impact cast sheet(CI30 type)
High impact Extruded sheet(EI25 type)
Altuglas ShieldUp
Contrary to impact PMMA made with classical technology, temperatureincrease does not cause haze
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Example of haze visual difference at high T°
Visibility of a picture through 3 mm sheets heated in oven at 80°C.Left = classical high impact cast sheet,
Right = ALTUGLAS® SHIELDUP cast sheetAutomotive glazing is possible
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ACRYLIC SHEET
Altuglas ShieldUp : very high impact resistance, even at low temperature
28_10_11 15_44.MOV
Cast impact PMMA, 4 mm ShieldUp, 3.5 mm
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Scratch and abrasion resistance
Scratch (Erichsen Test) Abrasion (Taber Test)
Evolution of Haze Vs number of cycles
0,00
5,00
10,00
15,00
20,00
25,00
30,00
35,00
40,00
0 10 20 30 40 50 60 70 80 90 100
nb cycles
haze
SHIELDUP PC
Stone ST11-2
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ACRYLIC SHEET
Stress cracking resistance (EN 13359, Isopropanol 2 5%)
0
20
40
60
80
100
120
140Extr
uded
, std
Extrud
ed, h
igh im
pact
Cast,
stand
ard
Cast,
high
impa
ct
Cast,
Nanos
tructu
red
Tim
e to
cra
ze in
s
Unmet Chemical Resistance
SHIELDUP
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Unmet Chemical Resistance
Acetone Test
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20
30
40
50
60
70
80
90
0 500 1000 1500 2000 2500 3000 3500
Stiffness (Flexural Modulus MPa)
Impa
ct s
tren
gth
U-C
harp
y(k
J/m
²)
Usual range highimpact castsheets
• Cast sheets with unmet impact properties can be made in a large range of moduluswhile keeping optical properties and T resistance
A large range of Modulus / Impact balance achievable
ShieldUp
Achievable range with Arkema Technology
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Easy to thermoform � high design flexibility
Altuglas ShieldUp sheet can be easily processed by thermoformingor bending at high temperature
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excellent UV Resistance (similar to standard HI PMMA)
3 mm sheet
UV study : WOM CI35 ; Renault D27-1911
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TDS of ALTUGLAS® SHIELDUP Cast Sheet
Description : Plaque PMMA nanostructuré à haute résistance au choc et très haute résistance chimique Caractéristiques déterminées pour des plaques incolores d’épaisseur nominale 3mm :
ShieldUP Caractéristique Méthode Unité Valeur Densité ISO 1183 1.17 Absorption d’eau ISO 62 % 0.36 Module en flexion ISO 178 MPa 2300 Résistance à rupture en traction*
ISO527 MPa 50
Allongement à rupture en traction*
ISO527 % 10
Choc charpy non entaillé
ISO 179 2eU KJ/m² 50
Choc Charpy entaillé
ISO 179 1eA KJ/m² 2.8
VICAT (50N) ISO 306 °C 106 Transmission lumineuse
ASTM D1003 % 92
Haze ASTM D1003 % < 1 * : 5 mm/mn
Les plaques sont livrées avec une protection de surface entre deux films de polyéthylène. Les tolérances d’épaisseur mesurées selon la norme ISO 7823-1, 2003 sont de 0.1 x épaisseur + 0.4 mm.
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ACRYLIC SHEET
ALTUGLAS® SHIELDUP cast Sheet : possible applications
Thanks to its new set of key properties, the ALTUGLAS®SHIELDUP Cast Sheet offers new possibilities of use in applications like :• Automotive :
• Sunroof or panoramic roof
• Rear quarter window
• Internal part
• Safety glazing : motorbike windshield, hockey rink, bulletproof , …
• Photovoltaic, solar panel
• Lighting
• POS
• …
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ACRYLIC SHEET
ALTUGLAS® SHIELDUP cast sheet for automotive glazing
In automotive glazing, the ECE R43 (Appendix 14) regulation is the reference in terms of tests to pass. Main requirements are resistances to impact, abrasion, humidity, chemicals and fire, weathering and opticalproperties.
ALTUGLAS® SHIELDUP has successfully passed the R43 tests :
panoramic sunroof Rear quarter window
Not coated Altuglas ShieldUp OK Not OK*
Coated Altuglas ShieldUp OK OK
* abrasion issue
New vehicles will be shortly equipped with ALTUGLAS® SHIELDUP
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ACRYLIC SHEET
R43 chemical resistance test
scratches + whiteningOKIsopropanol
Crack + whiteningOKAcetone
scratches + whiteningOKAntifreezesolution (Glycol)
scratches + whiteningOKGlazingwashingsolution
scratches + whiteningOKGasoline
Extruded PCAltuglasShieldUp
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ACRYLIC SHEET
ALTUGLAS® SHIELDUP sheet : Better scratch resistance compared to other existing solutions
Scratch profiles (Erichsen test at 2N)
-10000
-8000
-6000
-4000
-2000
0
2000
4000
6000
8000
10000
0 100 200 300 400 500 600 700
width (µm)
Hei
ght (
nm)
PC Lexan
Weatherable & UV resistant PC (Tuffak XL)
PC coated Margard
PC coated Margard
Shield 7 (CRP sheet CHI25)
� ALTUGLAS® SHIELDUP cast sheet presents the best resistance to deep scratch, even better than a coated PC .
� In addition to a visible deep scratch, the cracking of the coating at the surface of the coated PC sheet could lead to bad weathering (yellowing) and possible brittleness issue.
ALTUGLAS® SHIELDUP
PolycarbonateCoated polycarbonate
Cracking of the coating !
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ACRYLIC SHEET
ALTUGLAS® SHIELDUP sheet : source of weight gain versus glass
Glass density : 2.53 PMMA density : 1.17
Example : case of a 1 m², 6 mm sunroof
15.2 Kg 7 Kg
theoretical weight gain by using PMMA :
54%
�Reduced fuel consumption (10% weight gain in a vehicule ~ 6-7 % fuel savings)
�longer driving autonomy for electrical vehicles
�Reduced CO2 emissions (Europe current target < 130 g/km)
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ACRYLIC SHEET
FUNCTION INTEGRATION IN ALTUGLAS SHIELDUP SHEET
• It is possible to integrate in the ALTUGLAS SHIELDU P sheet new functions that can be of interest for applications like lighting or automotive glazing :
•Solar Insulation
•Edge lit Technology : ELIT
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ACRYLIC SHEET
Function integration in ALTUGLAS SHIELDUP : Solar Insu lation
• Solar Insulation
0
10
20
30
40
50
60
70
80
90
100
0 500 1000 1500 2000 2500 3000
wave length (nm)
trans
mis
sion
(%)
CI clear sheet
Solar insulation fomulation CIsheet
Solar spectrum
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ILLUSTRATION OF ELIT ALTUGLAS SHIELDUP
Standard PMMA sheet
ELIT ALTUGLAS SHIELDUP sheet
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Altuglas ELIT
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Conclusions
ALTUGLAS® SHIELDUP PMMA cast Sheet :
• A Worldwide Première
• Innovative balance of properties :• High impact resistance• More transparent and lighter than glass• Unmet chemical resistance • Very high scratch resistance• Naturally resistant to UV• Easy to process (thermoforming), high design flexibility• Possibility to integrate functions (Solar insulation, Edge lit, Fluo, …)• Suitable with many coatings, silk-screen printing, bonding systems
• A new candidate of choice for demanding applications
• The first commercial sheet of a new generation of PMMA (nanostructured)
uncoated and coated ALTUGLAS® SHIELDUP
Density
Transparency
Abrasion resistance
scratch resistance
Impact strength
Stiffness
Chemical Resistance
UV resistanceCoated ALTUGLAS® SHIELDUP
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ACRYLIC SHEET
PerspectivesAltuglas ShieldUp cast sheet can only processed by thermoforming.
Altuglas will enlarge shortly its nanostructured PMMA product offer by developing some resins suitable with injection molding and (co)extrusion processing technologies.
Still based on the same Arkema proprietary technology, the future resins referenced Nanostrength will offer the same key properties of Altuglas ® ShieldUp :
• Impact and transparency whatever the temperature• Very high chemical resistance • Durability and optical properties similar to standard PMMA
A large range of Impact/Stiffness balance will be achievable :
• From very soft ( 500 Mpa / “Unbreakable”) to rigid PMMA (2500 MPa / moderate impact resistance)
The first industrial products will be available in a close future.
