composite applications for marine -...
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DSM Composite Resins
Composite applications for MarineFebruary 28 – March 01 2005
Moscow, Russia
Fabienne Grandchamp
Expertise Manager RTM Marine
Ron Verleg
Expertise Manager Export
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DSM Composite Resins
Agenda
• Welcome• Short introduction DSM & DSM Composite Resins• Basics on unsaturated polyesters chemistry• Marine Application
• Mold Making• Blistering of GRP boat hull due to osmosis• Gelcoat• Tiecoat• Structural resins for hull and decks – HLU / SU applications• Structural resins for hull and decks – injection techniques
• Superb adhesive for marine applications• Case histories
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DSM Composite Resins
Globally active “multi-specialty” chemical companyGlobally active “multi-specialty” chemical company
• More than 200 locations, approx. 25,000 employeesMore than 200 locations, approx. 25,000 employees
Leadership positions in ~75% of the portfolioLeadership positions in ~75% of the portfolio
R&D spent appr. € 300 millionR&D spent appr. € 300 million
Solid balance sheetSolid balance sheet
• Net debt < € 500 mlnNet debt < € 500 mln
DSM today
Life Life Science Science ProductsProductsPerformance Performance
MaterialsMaterials
Industrial Industrial ChemicalsChemicals
OthersOthersDSM NutritionalDSM Nutritional
ProductsProducts2003 key data*:Sales : € 6,050 millionEBITDA: € 723 millionEBIT: € 294 million
* incl. one quarter DNP 2004 E
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DSM Composite Resins
Food
19%
Automotive/Transport
9%
Pharma
18%
DSM’s key end markets
Building & Construction
16%
E & E
6%
Life Science Products
Industrial Chemicals
Others
DSM NutritionalProducts
Performance Materials
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DSM Composite Resins
DSM Worldwide
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DSM Composite Resins
DSM Performance Materials
End-markets
Sales 2003 € 1.6 bn
Electrics & Electronics
Packaging
Metal & machine
Other
Building & constructionFibres/textiles
Transport/ automotive
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Welcome to
DSM Composite Resins
Leading the Composite Resins Industry by
focusing
on Customer’s
needs for Success
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DSM Composite Resins
• European market leader in unsaturated polyester resins• Global leader in sizings and binders
• Euroresins is part of DSM Composite Resinsand a leading distributor group in Europe
Product lines• Unsaturated Polyester Resins• Gel coat Products• Polymeric Plasticizers• Sizings & Binders
• Sales: > EUR 400 million• Employees: > 750 people
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DSM Composite Resins
• Schoonebeek (NL)
• Zwolle (NL)
• Ludwigshafen (D)
• Nanjing (CHN)
• Compiègne (F)
• Filago (I)
• Warsaw (P)
• Augusta (USA)
• Schaffhausen (CH)
Our presence in the world
• Ellesmere • Port (GB)
• Como (I)
• Tarragona (ES)
• Deeside (GB)
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DSM Composite Resins
Polyester resins chemistry
Polyesters are polymers resulting of the polycondensation (or poly esterification) at high temperature between multifunctional acids and alcohols.
Most of the times di-acids and di-ols (2 functionalities) are used :
HOOC - R - COOH + HO – R’ – OH polyester + water ∆T
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DSM Composite Resins
Polyester resins chemistry
To obtain unsaturated polyesters, at least one of the components must
contain a double bond ( C = C ) able to react with a vinylic or
acrylic monomer :
O
OO C C
CHHC
Maleic anhydride
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DSM Composite Resins
Polyester resins chemistry
Many different diacids and glycols types are used in the polyester polymer, providing a wide range of properties.
Main acids :
COOHHOOCCOOH
HOOC
COOH
COOH
Orthophthalic acid/anhydride Isophthalic acid Terephthalic acid
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DSM Composite Resins
Polyester resins chemistry
Main glycols
HO - CH2 - CH2 - OH
HO - CH2 - CH2 - OH
CH3
HO - CH2 - C - CH2 - OH
CH3
CH3
CHO - C - C - O
CH3
CH3
O - C - C - OH
CH3CH3
Neopentyl glycol
(Di-)Ethylene glycol
(Di-) Propylene glycol
Propoxylated bisphenol A
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DSM Composite Resins
Polyester resins chemistry
DCPD (dicyclopentadiene)
O
OH
OH
O
+
OO
O
OH
To comply with regulation concerning styrene emission we developped resins based on DCPD . Resins with less styrene
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DSM Composite Resins
Polyester resins chemistry
Vinylester
Epoxy + (Meth)acrylic acid Vinyl ester∆T
∆T
O O
C - C - R - C - C + HO - C - C = C
O
O O CC
C
OHOH
C = C - C - O - C - C - R - C - C - O - C - C = C
Vinylester Urethane
Hydroxyl polyester + Hydroxyl acrylate Vinylester urethane ∆T
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DSM Composite Resins
Polyester resins chemistry
Unsaturated polyester resins- Ortho-, iso- and terephthalic resins- DCPD resins
Vinyl ester resins- Epoxy-acid
Vinyl ester urethane resins- Isocyanate-hydroxyl (meth)acrylate
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DSM Composite Resins
End of introduction
Start of the marine related topics
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DSM Composite Resins
Marine market – Production of GRP boats
DSM systems for every stage :
Mold making
Hull and Deck construction
Bonding and fixing
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DSM Composite Resins
Marine application - Mold Making
Traditional mould making• Double gel, tissue, low wt / tex first layer• Structural - < 2 x 450 CSM / day.• Exotherm must be minimised.• Typical 6-10 days per mould.
WHY SUCH A SLOW PROCESS ?• PE’S shrink typically 8% volumetric, 1% laminate linear.• High build = High exotherm = Rapid, uncontrolled shrinkage =
Distortion of pattern and mould = Loss of original dimensional accuracy.
• Built-in stresses = Difficulty in mould release from pattern
TIME CONSUMING
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DSM Composite Resins
Mold Making : How to improve
SHRINKAGE STD POLYESTER LIQUID LP PE - ADDITIVE IS COMPATIBLE
GELLED LP PE - ADDITIVE PHASES OUT
EXOTHERM EXPANDS THERMOPLASTIC DROPLETS, SHRINKAGE OF PE IS COUNTERACTED
SHRINKAGE ELIMINATION BY LOW PROFILE TECHNOLOGY
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DSM Composite Resins
Mold Making : the solution
• Exotherm is important - More is better.• Special catalyst needed - Counteracts residual Benzaldehyde ( cure /
odour).• Effective phase out of LP additive is evident from colour change.
HOW
Euroresins RAPID TOOLING SYSTEMA LOW SHRINK MOULD LAY UP SYSTEM
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DSM Composite Resins
Mold making – RTS
RTS – STAGES OF PROCESS
• Double Gelcoat (ISO / VE)
• (Surface tissue)
• 1 Layer low tex light weight MAT / ERTS Resin
• 5 X 300 GM layers / ERTS Resin (4mm)
• Allow exotherm to subside (2 hrs)
• 4 X 450 GM layers ( 5mm)
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DSM Composite Resins
Mold making – High standard molds
RTS FOR HIGHER DEMAND MOULDS
• Double gelcoat ( VE)
• 1 layer low tex light weight MAT / VE TOOLING RESIN (ATLAC 580 ACT). Cure overnight
• 4 X 450 GM layers / ERTS Resin (5 mm)
• Allow exotherm to subside (2 hrs)
• 4 X 450 GM layers ( 5mm)
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DSM Composite Resins
Mold making steps
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DSM Composite Resins
Mold Making : Technical advantages of the RTS
TOTAL MOLD MAKING TIME REDUCED TO 1-2 DAYS EASY RELEASE FROM PATTERN EXCELLENT DIMENSIONAL REPRODUCTION FULLY PRE FORMULATED - JUST ADD CATALYST (MAJOR ADVANTAGE
OVER COMPETITIVE SYSTEM SYSTEM) MIX IS STORAGE STABLE MINIMAL SLIP / DRAIN FROM VERTICAL SURFACES HIGH HDT CAN BE USED FOR HLU / SU AND RTM MOULDS OFFERS EXCELLENT SYSTEM POTENTIAL WITH 8397-W-0100 VE
TOOLING GEL