pliogrip structural adhesives - tecnologia de...

Ashland Performance Materials

Pliogrip Structural Adhesives Acrylic Adhesive for Composite Bonding

November 7, 2012

Michael Barker

Research Fellow


2

Commercial

Units

Ashland

Specialty

Ingredients

Ashland

Water

Technologies

Ashland

Performance

Materials

Ashland

Consumer

Markets

Leading

Products &

Services

#1

cellulose ethers,

global leader in

vinyl pyrrolidones

#1

specialty

papermaking

chemicals

#1

unsaturated

polyester resins

and vinyl ester

resins

#2

U.S. franchised

quick-lube chain,

Passenger-car

motor oil

Sales1 $2.7 billion $1.9 billion $1.7 billion $2.0 billion

1 (Pro Forma) for 12 Months Ended Mar. 31, 2012

Four Strong Businesses


3


Key Benefits to Critical Applications

Composites

Lightweight High Strength

Durability Corrosion Resistance

Adhesives

Strength Durability

Removability Food Safety

Elastomers

Pressure Sensitive

Wear Resistance

Durability

Adhesion


4

Our Global Presence


5

Outline

Adhesive Overview

Acrylic Adhesive Technology

Pliogrip Acrylic Adhesives

Marine Case Studies


6

Pliogrip Structural Adhesives

45 years of experience in bonding some of the most

demanding applications i.e. automotive, heavy truck,

marine and general assembly

Trusted and chosen by dozens of leading OEMs for

bonding of composite parts

Today’s overview

Pliogrip 1000 acrylic adhesive & marine case

studies

and many others…


7

Definitions

An adhesive is a non-metallic substance that is able to bond the substrates by adhesion (surface forces) and cohesion (internal rigidity)

Structural adhesives represent a class of chemical bonding agents where the strength of the adhesive is greater than the strength of the substrates that are bonded together

The bonded structure must perform under a variety of extreme environmental conditions and load


8

Definitions (cont.)

Open Time

The time after mixing a two component adhesive in which the wetting properties of the adhesive are still sufficient to build proper adhesion

Cure time

The time required, after joining

the substrates, to build sufficient strength in the bond line to allow further processing or transportation of the part

Str

ength

Opentime

Handling strength

Operational strength

Final strength

TimeMixing

Str

ength

Opentime

Handling strength


Final strength

TimeMixing

Str

ength

Opentime

Handling strength


Final strength

TimeMixing


9

Advantages of Adhesive Bonding

Surface distortion minimized

Stress is distributed uniformly over bond-area

Suitable for bonding a variety of materials

Enables bonding of dissimilar materials

Very strong, age- and crash-resistant bonds

Excellent chemical resistance

Proven technology

Increased productivity


10

Definitions

Pot Life

Open Time

Cure Time Time required for the adhesive to reach its ultimate strength (varies with temperature, chemistry and substrate)

Green Strength Time required for the adhesive to achieve green strength allowing further handling of the bonded part (varies with temperature and chemistry) typically 0,35- 0,7 MPa

Time after mixing the two parts in which an adhesive must be applied

Timeframe after adhesive application to achieve good wetting of the second part

2-Part Adhesive Reactive components are kept separate until ready for use


11

Adhesive Types Vs. Bulk Mechanical Properties Tensile

Str

ength

[M

Pa]

Elongation [%]

10

20

30

40

100 200 300 400

Phenolics

1-& 2-k Epoxy

2-k-Acrylics

Structural 2-k-Polyurethane

Elastic Adhesives / Structural Sealants


12

Adhesion Cure-

type

Adhesive Selection

PLIOGRIP® Structural Adhesives


13

Acrylic Adhesive Technology

Common uses – “open mold” composites, gel coats,

bare metals e.g. boats and truck cabs

Very fastest fixture time at RT but cannot be heat

accelerated

Resists corrosion in bare-metal bonding

Bondable open time from 5 to 80 min

Very high elongation

6 month shelf life

Flammable with acrylic odor / VOCs

Tensile: 21- 28 MPa

Elongation: ~ 70-150%

Modulus: ~365- 410 MPa

Viscosity: 225 – 250 Pa s

Mechanical Properties

+

Free Radical Monomer

//upload.wikimedia.org/wikipedia/commons/9/9c/Initiation_-_primary_recombination.png


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Pliogrip Acrylic Adhesives


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PLIOGRIP®

Adhesive

PLIOGRIP®

Curative

Open

Time

(minutes

at 22C)

Fixture

Time

(minutes

at 22C)

Features & Benefits

1000 MARINE

(drum only)

1000

1040 40 80

High-body, long open-time, low-

boil product for stringer & deck-to-

hull bonding. For use on FRP and

gel coat surfaces.

1060 60 120

1080 80 160

1100 140 280

1000c GENERAL

INDUSTRIAL

(drum or

490ml

cartridges)

1005c (1003LV/1202) 5 - 8 10 – 15 Faster fixture times for smaller

jobs. Exceptional performance

on FRP, aluminum, stainless steel,

CRS, ABS, PC, and other

substrates.

1010c (1003LV/1202) 8 – 13 20 – 25

1020c (1002LV/1201) 16 – 24 40 – 50

1035c (1001LV/1201) 30 – 40 70 – 80

• Significantly less boil than competitive acrylic adhesives

• Increased productivity through long open times yet faster fixture times

• Reduces bond-line read through

Pliogrip 1000 10:1 Acrylic Adhesive

Pliogrip Acrylics have a 6 month shelf life from date of shipping


16

Pliogrip Acrylic in Marine Applications

16

Stringer Bonding, Deck-to-Hull, Liner, Bulkhead

Replaces “glassing in” (lamination) or bonding paste

significant time savings (no sanding / prep)

higher elongation, flexibility,

better fatigue properties

Pliogrip 1000

Very long open times (up to 140 min +)

High body and gap-filling

Pliogrip 1000c

Faster cure times

Cartridges available

Enhanced performance on bare metals


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20

40

60

80

100

120

140

160

0 30 60 90 120 150 180 210 240

Tem

pera

ture

(C

)

Time (minutes)

Pliogrip 1000 Cure vs. Mix Ratio

Pliogrip Adhesive

8:1 by volume 10:1 by volume 12:1 by volume

Open

Time

Fixture

Time

Open

Time

Fixture

Time

Open

Time

Fixture

Time

Pliogrip 1000/1040 47 min 70 min 57 min 81 min 74 min 103 min



Pliogrip technologies are

adaptable to meet various

processing needs, thus

eliminating demand for different

adhesive systems


18

Pliogrip 1000c Bonding Vs. Substrate

5,3 MPa 15,3 MPa

Pliogrip 1020c Structural

Acrylic Cartridge Adhesive

Lap Shear Samples

Fiber Tear on FRP and Cohesive

Failure on Metal with

No Surface Preparation

FRP to Gelcoat

Fiber Tear

765 psi (avg)

5,3 MPa

Stainless Steel 304

Cohesive Failure

2217 psi (avg)

15,3 MPa

FRP to FRP

Fiber Tear

500 psi (avg)

3,45 MPa

Aluminum 6061-T6

Cohesive Failure

2157 psi (avg)

14,9 MPa


19

19

Pliogrip 1000c Has Better Sag Resistance

1,0 cm 0,13 cm 0,38 cm

Pliogrip has less sag on vertical applications. The adhesive will not move out of

the glue line and cause excess clean up or result in bondline starvation

Competitor A

Competitor B

B A


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20

-40ºC Cold Side Impact Performance

Standard - GM9751P • 60 in-lb is “perfect score” • achieving a rebound

60

53

60

15

56

22

48

23

0 10 20 30 40 50 60

Energy Absorbed (in-lb)

FRP

CRS

SS-304

AL 6061 T6

Su

bstr

ate

Teste

d

PG 1005c Competitor XX420

Excellent bond performance on a variety of metal and

composite substrates, exceeded competitive products


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Pliogrip 1000 in FRP Bonding

PLIOGRIP Exhibited 100% Fiber Tear In All Cases

PLIOGRIP

Competitor 1

Competitor 2

Competitor 3

Lap

Sh

ear

Str

eng

th

MPa

Tested on standard composites used in the marine market -

Lap shear performance meets or exceeds the competitor products


22

Adhesive

Test Temperatures

At 20C At 31C

Open Time

of a 5 cm

Bead

(min)

Time to

Strength

Build in a

0,32 cm

Bond (min)

Open Time

of a 5 cm

Bead

(min)

Time to

Strength

Build in a

0,32 cm

Bond (min)

Pliogrip

1000/1060 78 97 30 54

Competition 80 200 30 110

Pliogrip 1000/1060 has a dramatic advantage over Competition

Improved Cycle Time & Ability to Process the Part Sooner

Pliogrip 1000 Vs. Competition Strength Build

1. As measured side-by-side in Ashland Inc. laboratory

2. Strength build is defined as when .7 MPa cross peel is reached


23

23

Pliogrip 1000 - Shrinkage & Boil

PLIOGRIP 1000

Bulk

Cartridge

Less Boil and Shrinkage with PLIOGRIP 1000 – Pliogrip has more durability within

the bond line resulting from the lack of voids and stress cracks, also may help

reduce bond line read through

Competitor 1

Competitor 2 PLIOGRIP 1000


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Pliogrip Acrylic Application Methods

2-part “catalyzed” structural adhesives must be mixed

together to start the cure process

Meter Mix Dispense Equipment

(Used with drums, or pails) Cartridges

Or HAND-MIX

With pallet & spatula


25

Case Studies


26

Advantages of Acrylic Adhesive

Stronger and better adhesive than bonding paste

Modulus and elongation result in tougher more fatigue-resistant joints

Acrylic bonds to FRP and gelcoat without sanding or abrasion

Cost of sandpaper

Reduce labor

Reduce dust from sanding

Reduce cleanup of dust

Faster application if using mix-dispense equipment

Faster cure than bonding paste

Cycle time in molds

Acrylic Adhesive vs UPR Bonding Paste

26


27

Acrylic Adhesive is Stronger than UPR Bonding

Paste on FRP

Room Temp

Lap Shear

Petrol/Gasoline Immersion

Lap Shear

Strength

(MPa)

Fiber Tear

(%)

Strength

(MPa)

Fiber Tear

(%)

PG1000 6,0 97% 6,5 100%

UPR ISO Marine

Bonding Paste 3,4 19% 2,7 14%

1. Surface preparation: dry wipe / no sanding

2. Substrate UPR FRP

3. Immersion in petrol/gasoline for 1 week at 23ºC


28

Case Study 13 Meter Fishing Boat

Miami, FL USA

Liner to Hull-Stringer Attachment

Change from UPR

bonding paste to Pliogrip

1000/1080


29

Case Study 13 Meter Fishing Boat – Miami, FL USA

Liner to Hull-Stringer Attachment

Change from UPR Bonding Paste to Pliogrip

Boat builder changed to Pliogrip 1000/1080 acrylic adhesive

for longitudinal stringer-to-liner joints and reduced extent of laminating reinforcement

50kg – 57 kg per boat @ 1,27 cm bond line thickness

Saved an average of 8 labor hours per boat Faster application of acrylic adhesive using GS Manufacturing TM mix-

dispense unit vs. bonding paste

Reduction of areas reinforced with lamination

Elimination of sanding and prep steps on adhesive joints

Stronger, tougher joints

Boat builder subsequently converted all product lines to Pliogrip


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Case Study 10 Meter sport fishing boats, Brasil

Stringer, Bulkhead, Deck-to-Hull

Stringer and bulkhead (existing models): boat builder uses 6-layer

lamination.

Deck-to-hull (existing models): boat builder uses combination of

lamination, 1-part MCU sealer, and screw fasteners.

Lamination

Prep consists of sanding and cleanup

Manual preparation of glass matt and tedious application of multi-layer

mat and laminating resin

Dust from sanding and unnecessary VOC in solvent wipe

Boat builder sought new attachment methods for it’s new model

Background


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Boat builder used Pliogrip 1010c and 1035c 490ml cartridges for

prototypes

Pliogrip 1010c used on deck-to-hull joint, eliminating 1-part MCU, and

reducing lamination on interior of joint and screw fasters on exterior of

joint

Cycle time reduced from 2 days to 40 minutes

Pliogrip 1035c used on stringer attachment, completely eliminating

lamination

Cycle time reduced from 5 days to 3 hours

Cycle would be further improved using drums and mix-dispense

equipment



Solution


32

32



27 PG1035c carts &

6 PG1010c carts

were used for

stringer (approx 15

kg)

Adhesive application

time 30 minutes,

plans to get faster

on next boat

IPA wipe employed

as prep-step (dust)


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Pliogrip 1000 Summary

Fast Fixture Times

Low Boil

Over 13,8 MPa lap shear strength with cohesive failure on bare aluminum, stainless steel, CRS

Achieves fiber tear on FRP and gel coat without prep

Excellent bare metal performance (Pliogrip 1000c)

Commercial applications in marine, bus/coach, and heavy truck

Displaces “glassing in” or bonding paste

Significant time savings (no sanding / prep)

High elongation, flexibility, excellent fatigue properties

Available in cartridge & bulk


34

Ashland – Produtos para Náutica

GEL COAT

RESINAS POLIÉSTER

& VINIL-ÉSTER

Beneteau, France

Chaparral, USA

Sea Ray, USA

ADESIVOS

ESTRUTURAIS

RESINAS COM

RETARDÂNCIA Á CHAMA


David Britto – 07/11/2012


35

MaxguardTM LE/33LE com tecnologia LE baixa emissão de estireno com superior qualidade.



36

MAXGUARD® LE/33LE com Patente da Tecnologia LE

Gelcoat MAXGUARD premiado

MAXGUARD NP

com a tecnologia LE foi eleito

como gelcoat mais importante

para o sucesso futuro

da indústria plástico reforçado!

INDUSTRY

AWARDS

Valores dos testes informados nesta apresentação são valores médios de diversos testes.


37


INDUSTRY

AWARDS

Tecnologia de baixa emissão

de estireno


38


INDUSTRY

AWARDS


de estireno

Gelcoat normal

• Polímero normal com

baixa compatibilidade

com estireno, resulta

em gelcoat com

excesso de estireno

= estireno


39


INDUSTRY

AWARDS


de estireno

Gelcoat com a tecnologia LE




em gelcoat com

excesso de estireno

= estireno

• O novo polímero de alta

compatibilidade com

estireno, significa baixo

teor de estireno no

gelcoat.

= estireno


40


INDUSTRY

AWARDS


de estireno

Emissão de estireno medido em cabine de pintura




em gelcoat com

excesso de estireno

= estireno

• O novo polímero de alta

compatibilidade com

estireno, significa baixo

teor de estireno no

gelcoat.

= estireno

1200

Gelcoat com 1000

Tecnologia LE

800

gelcoat normal Q

ua

ntid

ade

ap

lica

da

(m

g/s

)

600

400

200

0

0 10 20 30 40 50 60 70

Tempo (min)


41

MAXGUARD® LE/33LE com Patente da Tecnologia LE Emissão de estireno e rendimento medido na cabine de pintura.

Gelcoat com Gelcoat Standard

Tecnologia LE

Teor de estireno 28% 39%

Tempo de aplicação 194 sec 187 sec

Massa pulverizada* 3.0 kg / 6.6 lb 3.0 kg / 6.6 lb

Massa no molde* 2.7 kg / 5.9 lb 2.4 kg / 5.3 lb

*escala Eficiência na Transferência 90% 80%

Emissão durante a Pulverização** 3.6% 7.0% **IR

Emissão Total** 6.7% 13.6%

Redução de 50% na emissão de estireno.


42

MAXGUARD® LE/33LE com Patente da Tecnologia LE Emissão de estireno medido na produção de um barco de 36 pés.

100

80

60

40 M

ed

içã

o d

e E

stire

no

no

du

to d

e

20

exa

ustã

o (

pp

m)

0

0 10 20 30 40 50 60 70

Tempo (min)

Gelcoat com Tecnologia LE gelcoat normal


43

MAXGUARD® LE/33LE com Patente da Tecnologia LE Resistência ao amarelamento medido pela QUV-A na FMC II

5

4

3

2

1 Am

are

lam

en

to (

DY

B)

0

0 250 500 750 1000

Tempo (h)

Gelcoat com tecnologia LE gelcoat normal

Redução de 50% no amarelamento


44

MAXGUARD® LE/33LE com Patente da Tecnologia LE Retenção de brilho medido pela QUV-A com ângulo de 20°

100

80

60

40

20

Brilh

o (

%)

0

0 250 500 750 1000

Tempo (h)


Aumento de 15% na retenção de Brilho


45

MAXGUARD® LE/33LE com Patente da Tecnologia LE Contração linear medida de acordo com a norma ASTM D 2566

100

80

60

40

20

Brilho (%)

0

0 250 500 750 1000

Tempo (h)


2.5

2.0

1.5

1.0

0.5

Co

ntr

açã

o (

%)

0


Redução de 30% na Contração


46

David Britto


47

David Britto


48


100

80

60

40

20

Brilho (%)

0

0 250 500 750 1000

Tempo (h)


2.5

2.0

1.5

1.0

0.5

Co

ntr

açã

o (

%)

0


Beneteau, France

Chaparral, USA

Sea Ray, USA


49

Soluções em resina para o mercado náutico


50

Soluções em resina para o mercado náutico

• Resinas de Laminação • Resinas de Infusão

AME 5100 (Resina Premium para Cascos e Skin Coat) AME 6100 INF (Vinil-Éster Premium)

AME 2100 AME 5100 INF

AROPOL Q65471 AME 2100 INF

ENVIREZ L 86300 (“Green” – Fonte de Recurso Renovável) AROPOL Q 65471 INF

• Solução para Skin Coat (Superfície isenta de marcações)

• Peças Pequenas (RTM)

AROPOL NLN 71500 INF AME VPRO AME 5001 + ARAZYN 13.0 (Gel VE Barreira Química) (Resina VE para Skin Coat)

ENVIREZ Q 11500 (Green)

• Resinas para Off-Shore & Tanques de Combustíveis

DERAKANE 510 N e 510 C

Hetron™LB 6806-182

MODAR 814A


51

Resinas para Laminação / Skin Coat

•Escolha dos produtos depende das necessidades requeridas por cada cliente. P

reço

•All MACT Compliant

•Uso em qualquer parte da embarcação.

AME 5100 T25 Premium VE. Grande combinação

de força e aparência

AME 2100 T25 Resina VE modificada para uso geral. Excelentes

propriedades mecânicas

AROPOL Q 65471 T25 Blenda de resinas com alto HDT, baixíssima contração

e excelente acabamento superficial

Desempenho


52

Resinas para Infusão

•Escolha dos produtos depende das necessidades requeridas por cada embarcação P

reço

•Uso em qualquer parte da embarcação

AME 6100 INF Premium VE, altíssimas propriedes físicas e HDT

Excepcional resistência á fadiga.

Indicada para barcos de alto desempenho

AME 5100 INF Premium VE. Grande combinação

de força e aparência

AME 2100 INF Resina VE modificada para uso geral. Excelentes

propriedades mecânicas

AROPOL Q 65471 INF Blenda de resinas com alto HDT, baixíssima contração

e excelente acabamento superficial

Desempenho


53

AME 2100 / AME 5100 / AME 6100 - Resinas Vinil-Éster

• Características

– Oferecer aos nossos clientes resinas Vinil-Éster com flexibilidade de opções,

atendendo todos os níveis de exigência técnica.

– Podem ser utilizadas em Laminação, Infusão e Skin Coat.

– Baixa emissão de estireno.

– Disponíveis também nas versões de INFUSÃO.

• Vantagens

– Melhores Propriedades que resinas disponíveis no mercado.

– Variados níveis de Desempenho e Custo, adequando-se as necessidades de

cada cliente.

– Longa história de sucesso em Náutica.

– Alto HDT e Propriedades Mecânicas.

– Elevada Resistência á Fadiga.

Disponível em estoque


54

Solução de Alto Desempenho para Skin Coat

Skin Coat

AME V-PRO Vantagens

(Gel Coat Barreira Química) –100% Vinil-Éster – Uso acima ou abaixo

da linha d’água + – Elevada Resistência ao Blistering

– Excelente Acabamento Superficial AME 5100 – Eliminação Print Thru em Infusões

(Resina Vinil-Éster) – Contração Superficial Reduzida

– Aplicação com Gelcoteadeira e “Caneca”

– Baixa Emissão de Estireno


55

AROPOL Q 65471 – Resina UPR Spray/Infusão Premium

• Características – Blenda de Resinas Otimizadas para Aplicações Náuticas.

– Baixa Emissão de Estireno.

– Reduzida Contração.

– Disponível também na versão de INFUSÃO.

• Vantagens

– Melhores propriedades mecânicas que resinas Ortoftálicas Covencionais.

– Acabamento superficial melhorado e duradouro, devido á Baixa Contração e

ao alto HDT.

– Indicada para clientes que desejam um upgrade de desempenho sobre resina

de laminação usada atualmente.

– Processamento mais rápido devido ao rápido desenvolvimento de Dureza

Barcol.

Disponível em estoque


56

Resinas Low Profile para RTM

• Gama variada de produtos P

reço

• Todas as pequenas partes acima da linha d’água

AROPOL NLN 71500 INF Acabamento Superficial Premium

ENVIREZ Q11500 INF Excelente Acabamento Superficial – “Opção Green”

Fonte de Recurso Renovável

AROTRAN 6500 Low Profile Standard. Necessita de aquecimento do molde

Performance


57

AROPOL NLN 71500 INF

• Características AROPOL NLN 71500

– Resina para RTM Low Profile (“Contração Zero”).

– Versões para 12 e 22 minutos.

– Cura à temperatura ambiente.

– Indicada peças pequenas acima da linha d’água.

• Vantagens

– Acabamento “Classe A” – acabamento com nível automotivo.

– Menor pico exotérmico, limitando danos nos moldes.

– Aplicável a grande variedade de processos e peças.

– Preço competitivo.

– Permite excelente acabamento para peças com Gel Coat aplicado em ambas as

faces.

Caso de sucesso em fabricantes como Tiara, Viking Grady White


58

Resinas para Tanques de Combustíveis

• Ainda há confusão sobre o uso de tanques de combustíveis

em compósitos, quando expostos á presença de Etanol.

• Ashland possui duas resinas disponíveis e testadas

– Ambas foram certificadas sob a norma UL1316 para armazenamento de

combustíveis.

– Derakane 510N (INF)

Resina Premium que não requere pós-cura

– Hetron™LB 6806-182

Menor custo, mas requer pós-cura

– Disponíveis nas versões de Infusão e Laminação


60

60

Bus/Coach Application Example Cargo Doors, Large Coach Manufacturer in

Canada Mixed material cargo doors

• RTM, RTM lite, FRP, Stainless Steel, Bare Aluminum, and Bare Steel

Customer desired to reduce # of adhesives and improve cold impact

results

Pliogrip 1003LV/ 1202 acrylic tested on substrates

• GM 9751P -40⁰C cold side impact testing

Pliogrip acrylic bested competition and secured this cargo door

application


61

Experimental Details

1.Open time determined by time for 100g mass in a 5 cm jar to reach 40ºC; 5 cm jar simulates

a 5 cm diameter bead

2.Fixture time determined by time to peak temperature in a 0,3 cm thick bond line, which correlates with strength build in cross-peel testing.

3.Smaller quantities would result in a slower cure rate, larger quantities would result in faster cure rate

4.Data measured at 23ºC conditions, hotter or colder ambient conditions will affect result


62

MARINE PRODUCTS


David Britto – 07/11/2012

pliogrip structural adhesives - tecnologia de...

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