novel formaldehyde free technology for glass … formaldehyde free technology for glass fibers:...

© The Lubrizol Corporation 2009, all rights reserved

Novel Formaldehyde Free Technology For Glass Fibers:

Hycar® FF 26920 & Hycar ® FF26921

Building and Industrial Mat Meeting 5/19-5/21Dennis P. Butcher – Technical Market Manager

Lubrizol Advanced Materials

© The Lubrizol Corporation 2009, all rights reserved2

Formaldehyde Free Technology For Glass FibersFormaldehyde Free Technology For Glass Fibers

Saturation ApplicationFiltration

Wet-laid Fiberglass/ Industrial MatsDuct LinerCarpet Tiles


The Clean Air Act

California Proposition 65

ACGIH lists formaldehyde as suspected human carcinogenAmerican Conference of Governmental Industrial Hygienists

IARC Group 1 Human CarcinogenInternational Agency for Research on Cancer

Free formaldehyde level permissible is continuously being reduced by various regulations globally

European Union, California, New England States are forefront in reducing the limits on free formaldehyde on various substrates

California Air Resources Board – Wood Products

Reducing formaldehyde may allow potential of “Green Branding” for products using alternative technologies

US Green Building Council – LEED Certification

Drivers for Formaldehyde Free Technology


What does a binder need to do in industrial mat applications?

• Bind fibers• Provide structural integrity

– Dimensional stability and strength• Initially during manufacturing of mat product• In final composite

• Provide processability and product integrity– Resistance to:

• Solvents• Plasticizers• Petroleum based materials

• Provide application appropriate feel– Stiffness– Flex


How do we measure binder performance?

Dry Tensile Strength

Hot Dry Tensile Strength

Thermal Stability

Hot Wet Tensile Strength

Wet Strength

Plasticizer Resistance Tensile Strength

Mat Chemical Resistance


Overall Physical Performance Targets

Achieve similar or improved properties of crosslinked industry leading acrylic with a formaldehyde free system.

Overall Performance of leading acrylic + 2.5 pph melamine formaldehyde

High Dry Tensile Strength Good Hot-Dry Tensile StrengthHot-Wet Tensile Strength

Good wet/dry ratioPlasticizer Resistance Tensile Strength


ProductProduct TgTgooCC SolidsSolids pHpH ViscosityViscosity CommentComment

Leading Acrylic +29 49.0 5.5 60 cP

Can Modify with MF or UF Resin to Improve:

Hot Dry Tensile StrengthHot WetPlasticizer Resistance

Conventional Benchmark

Product commonly used in construction products alone and with crosslinking resins

Key Properties– Dry Tensile– Hot Dry Tensile Strength– Hot / Wet Tensile


Procedures for Testing BindersSubstrate: Whatman® Microfiber GF/A

Test Conditions:• Target LOI: 25% • Dry/Cure Conditions: 2 minutes at 375°F• Sample Conditioning: Samples conditioned for 24 hours at 70±1°F and 50%±2% RH• Crosshead speed for tensiles- 1”/min.• Avg. of 4 specimens• Tensiles recorded in lbs./in.

Dry Tensile• 1x 6 Sample • Gauge length – 4”

Hot-Dry Tensile• 1"x9" Sample - die cut• Gauge length - 7"• Samples placed in hot slot and tested after 1 minute at 375°F

Hot-Wet Tensile• Samples immersed 10 minutes in H2O at 180°F• Tested using same parameters as dry tensile

Plasticizer Soak• Samples immersed 2 minutes in Diisononyl Phthalate (DINP) at RT• Tested using same parameters as dry tensile


Glass Fiber Saturation Test Procedure• Substrate- Whatman Microfiber Grade:GF/A• Saturate substrate sheets with latex on Padder• Dry sheets in oven at 190°C/ 2 min.• Cut sample into strips and measure tensile properties

Padder Tensile Test


Dry TensileSystem Summary on Whatman Microfiber GF/A

25% Binder Level

11.45 11.37 11.48 11.6011.91

8.0

8.5

9.0

9.5

10.0

10.5

11.0

11.5

12.0

12.5

Leading Acrylic Leading Acrylic +2.5 pph MF

Hycar® FF 26920 Hycar® FF 26921 Hycar® FF 26921+ 2K

Tens

ile (l

bs/in

.)

Dry Tensile


Hot Dry TensileSystem Summary on Whatman Microfiber GF/A

25% Binder

3.9

5.25.8

6.7

5.5

0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0



Tens

ile (l

bs/in

.)

Hot Dry Tensile

28% Improvement


Hot Wet TensileSystem Summary on Whatman Microfiber GF/A

25% Binder

2.2

2.9

2.3

4.8

5.8

0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0



Tens

ile (l

bs/in

.)

Hot Wet Tensile

65-100%Improvement


Plasticizer Soak TensileSystem Summary on Whatman Microfiber GF/A

25% Binder

10.911.9 11.9

12.5

7.7

0.0

2.0

4.0

6.0

8.0

10.0

12.0

14.0

16.0



Tens

ile (l

bs/in

.)

Plasticizer Tensile


Composite Tensile ResultsSystem Summary on Whatman Microfiber GF/A

25% Binder

0.0

2.0

4.0

6.0

8.0

10.0

12.0

14.0

Dry Tensile Hot Dry Tensile Hot Wet Tensile Plasticizer

Tens

ile (l

bs/in

.)

Leading Acrylic

Leading Acrylic + 2.5 pph MF

Hycar® FF 26920

Hycar® FF 26921

Hycar® FF 26921 + 2K

Performance equaled or exceeded control in all cases


Based upon initial development work, additional studies were performed to better understand application properties and property development

1. Attempt to better quantify wet tensile improvement2. Examine wet tensile strength development as a function

of time3. Examine tensile strength development as a function of

temperature


Wet and Dry Tensile – 2 min cure @ 190ºC

Dry and Wet Tensile with % Retention

0.0

2.0

4.0

6.0

8.0

10.0

12.0

14.0

16.0

Leading Acrylic +2.5 MF

Hycar® FF 26920 Hycar® FF 26921 Hycar® FF 26921FF Xlink #1

Hycar® FF 26921FF Xlink #2

Sample ID

lbs/

in

0%

10%

20%

30%

40%

50%

60%

% re

tent

ion

wet

/dry

Dry TensileWet Tensile% Retention

35-60% improvement in wet/dry tensile ratio


Cure Rate Study - 190º

Cure Rate Study-Wet TensileWhatman Microfiber GF/A 25% LOI

0

1

2

3

4

5

6

7

0.5 1.0 2.0 3.0min.

lbs.

/in.

Leading Acrylic + 2.5 MF

Hycar® FF 26920

Hycar® FF 26921

Hycar® FF 26921-FFXlink #1

Hycar® FF 26921-FFXlink #2

ControlBetter wet tensile properties at equal or lower curing duration


Cure Temperature Study – 2 min.CURE STUDY - Wet Tensile on Whatman GF/A 25%LOI

0

1

2

3

4

5

6

7

100 125 150 191°C

lbs/

in.

Leading Acrylic + 2.5 MF

Hycar® FF 26920

Hycar® FF 26921

Hycar® 26921-FFXlink #1

Hycar® 26921-FFXlink #2

Control

Wet tensile strength improved under normal comparable drying conditions


Findings ………1. Formaldehyde free products showing improved tensile

properties on microglass over MF crosslinked Leading Acrylic system– Hycar® FF 26920 compared to control– Hycar® FF 26921 shows improved hot and wet tensiles

compared to control

2. Hycar® FF 26921 demonstrates improved cure response compared to control– Opportunity for energy savings?


Total Formaldehyde (ppm)

0

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

Leading Acrylic Leading Acrylic+

2.5 pph MF

Hycar®26920 Hycar® 26921 Hycar® 26921 -2K

Product ID

ppm

HC

HO

Total Formaldehyde (ppm)


HYCARHYCAR®® FFFF--26920 Formaldehyde Free System 26920 Formaldehyde Free System

Unique Benefits:Unique Benefits:• Formaldehyde Free System• Unsurpassed Hot Dry Tensile Strength• Self Cross-linking• 1K solution to a typical 2K system

Tg: +29°CViscosity: 105 cps (#2 @ 60rpm)pH: 8 – 9Solids: 44%

Solution Description:Solution Description:

Hycar FF-26920 is a one component system replacing the use of traditionalacrylic emulsion binder and melamine-formaldehyde cross-linker for a non-yellowing binder for most industrial use fiberglass nonwovens.

General SpecsGeneral Specs

Potential Applications:Potential Applications:

• Wet-laid • Fiberglass/ Industrial Mats• Duct Liner• Carpet Tiles• High Tech Filtration

Value Creation:Value Creation:• “Green” implications because of Formaldehyde Free system• Reduced emissions at substrate manufacturing process• Extended durability and usage life of substrate because enhanced hot

dry tensile strength

FiberglassFiberglassBuilding MatBuilding Mat


HYCARHYCAR®® FFFF--26921 Formaldehyde Free System 26921 Formaldehyde Free System

Unique Benefits:Unique Benefits:• Formaldehyde Free System• Unsurpassed Hot Wet Tensile Strength• Self Cross-linking

Tg: +29°CViscosity: 65 cps (#2 @ 60rpm)pH: 8 – 9Solids: 44%

Solution Description:Solution Description:

• Hycar FF-26921 is a one component system replacing the use of traditional acrylic emulsion binder and melamine-formaldehyde cross-linker to be used as a binder for most industrial use fiberglass nonwovens.

• For unsurpassed performance, additional non-formaldehyde component can be added

General SpecsGeneral Specs

Potential Applications:Potential Applications:

• Wet-laid • Fiberglass/ Industrial Mats• Duct Liner• Carpet Tiles• High Tech Filtration

Value Creation:Value Creation:• “Green” implications because of Formaldehyde Free system• Reduced emissions at substrate manufacturing process• Extended durability and usage life of substrate because enhanced hot

wet tensile strength

FiberglassFiberglassBuilding MatBuilding Mat


Thank You!

AcknowledgementsAshok Makati

Jamel LawrenceMatt Sciulli

Prachur BhargavaGary Anderle

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