Huntsman Products for the Metalworking · PDF file600 700 800 900 1000 Dissolved Cobalt (ppm)...

Huntsman Products for the Metalworking Industry 2005

Performance Products

AgendaHuntsman Corporation overview

Huntsman metalworking specialties and research activities

Surfactant Innovations – SURFONIC® MW-100 additiveLow Foam surfactantsDGA® agent – new registrationsBHEMA – TEA replacementAluminum and Magnesium studiesSURFONAMINE® MW-781 butoxypropyl amineJEFFAMINE® D-2000 defoamer


Huntsman Business Divisions

Advanced Materials Polyurethanes Performance

Products Pigments Polymers Base Chemicals

Design & Composites Engineering

Power & Electronics

Coatings, Construction & Adhesives

Rigids

Flexibles

Elastomers

TPU

Performance Specialties

Performance Intermediates

MaleicAnhydride &

Licensing

Titanium Dioxide

Polyethylene

Polypropylene

APAO

EPS

Ethylene

Propylene

Butadiene

Cyclohexane

Paraxylene

MTBE


Extensive Global Reach

And Technical Centers Close to the Customer

Major Integrated Manufacturing Sites


SURFONIC® MW-100 Additive

A versatile emulsifier for vegetable oils:

Inherently low foamingCompatible with phosphate esters for EPCan be used to formulate macro or micro emulsions that are very stableLow pour point (- 2°C) for easy handlingLow toxicity


Macro MicroEmulsion

Particle size of Microemulsionand Diluted Macroemulsion

SURFONIC® MW-100 Additive Emulsion Characteristics


Macroemulsion with SURFONIC® MW-100 Additive

Water99.00

MW-100 11.30 Soybean oil11.70

0.70 0.30

88.00

3

5

5

7

7

8

8

10

Falex Wear TestConditions:5 minutes conditioning15 minutes, 675 lbs direct load


SURFONIC® MW-100 Additive

Effect of Formulation on Torque @ 4000 PSISoybean Oil Based


Soybean Oil Microemulsionwith SURFONIC® MW-100 Additive

Microemulsion Phosphate ester

Phosphate esterMW 100

Soybean Oil

00

0 100100

100


Vegetable Oil-Based Soluble Oil

SURFONIC® MW-100 20 Emulsifieradditive

Canola Oil 70 Lubricity agentSulfurized fatty acid 4 EP agentAlkanolamide 3 Corrosion controlBiocide 2Other additives q.s. dye, etc.

Products of this type can be formulated at 20:1 to 100:1 (with adjustments to increase corrosion control).



Alkoxylated Surfactants

R - EO - POFo

amin

gFo

amin

g

IncreasingIncreasing Component SizeComponent Size


Tridecyl Alcohol Alkoxylate (5 EO, 12PO) Effect of nonionic/sulfonate ratio


TDA EOPO Effect of EO and PO on foam height, 40°C


Low Foaming SURFONIC® Surfactants

SURFONIC LF-18 surfactant: used as self-cleaning lubricant in machining operation prior to laser welding

SURFONIC LF-47 surfactant: general purpose low-foam applications

SURFONIC P1, P3, P5 and JL-80X surfactants: NPE replacement


Emulsifiers (Ethoxylates) SO, SSNPE SURFONIC® N surfactantsLAE SURFONIC L surfactantsBranched Alcohol SURFONIC DA and TDA surfactantsAlcohol EO/PO SURFONIC P and JL surfactantsFatty acid ethoxylates SURFONIC E400-MO surfactant

Low Foamers SO SS SY CLSURFONIC LF surfactants LF-18, LF-17, LF-47SURFONIC POA surfactants POA-L101, POA-17R2,

POA-25R2


Lubricity actives for synthetics SY, CLSURFONIC® POA-17R2, POA-25R2, POA-L101 and POA-L61 surfactantsSURFONIC LF-18 surfactantSURFONIC L4-29X surfactant

Coupling agents SO, SS, SYPropylene GlycolDipropylene GlycolSURFONIC L24-2 and L12-3 surfactants


Extreme Pressure Agents SS, SYPhosphate esters - SURFONIC® PE-2258, PE-533, PE-BP2 and PE-2188 surfactantsProvide anti-weld functionality

Lubricity Additives SO, SS, SY, CLAmidesPEG Esters - SURFONIC E400-MO surfactantReduce friction and heat load

Alkanolamines for alkalinity control SO, SS, SY, CLMEA, DEA, TEA, DGA® agent, alkylalkanolamines DMEA, MDEA, BHEMA


Specialty Amines

Amines provide alkalinity for corrosion control

Amines are often blended (primary + tertiary) for buffering

Certain amines may be useful in low-biocide formulations (especially branched etheramines)


CHH2N CH2

CH3

OCH2

CHNH2

CH3

x

CH2[OCH2CH(CH3)]NH2

CH2[OCH2CH(CH3)]NH2

CH2[OCH2CH(CH3)]NH2CH3CH2x

yz

x + y + z = ~5.3

JEFFAMINE® T-403 amine(XTA-771)

HOCH2CH2OCH2CH2NH2

HOCH2CH2NH2

(HOCH2CH2)2NH

(HOCH2CH2)3N

DIGLYCOLAMINE® agent

MEA

DEA

TEA BHEMA

(HOCH2CH2)2NCH3

Huntsman Amines for Metalworking

5-6JEFFAMINE® D-400 amine

2-3JEFFAMINE® D-230 amine

xProduct


Commonly Used Amine Derivatives

Carboxylate salts - buffering and lubricity

Boric acid salts and condensates - high pH buffer –bioresistant

Carboxamides - lubricity, secondary emulsifier, corrosion control

Acid phosphate salts - cleaning corrosion control (vibratory acid)


Industry Concerns Influenced by Amine Selection

Environmental, Health and Safety IssuesToxicityMisting and VolatilityRegistration Issues

Performance IssuesReserve AlkalinitypH StabilityCorrosion Protection (Ferrous and Non-Ferrous)Extending Tool Life (Lubricity, Cobalt Leaching)Concentrate Stability


Benefits of DIGLYCOLAMINE® Agent

DGA® agent has low acute toxicity and low toxicity to aquatic species, is non-mutagenic in in vitro systems, and has low nitrosamine potential

While DGA® agent is corrosive to the skin and eyes (similar to other strong primary amines), it is not a dermal sensitizer

Low volatility, pour point and viscosity of DGA® agent make for easy, safe handling.


Benefits of DIGLYCOLAMINE® Agent

Many amides and salts of DGA® agent are TSCA registered and are easy to make

DGA® agent is a strong primary amine that gives a cost-effective alkalinity boost and provides effective corrosion inhibition with low odor

DGA® agent has a low tendency to leach cobalt and copper from tooling

DGA® agent causes less staining of some Al alloys than other amines


DGA® Agent Developments

Castor oil amide was registered on TSCA 4/1/2004

Soya, Stearic and Isostearic amides – additional aquatic toxicity requested

Magnesium corrosion work


Registrations for Derivativesof DGA® Agent

TSCA 99-350 DGA® amide of Neodecanoic acid 212335-62-1TSCA 99-351 DGA amide of Coco Fatty acid 212335-59-6TSCA 99-352 DGA amide of Dodecanoic acid 20138-28-7TSCA 99-353 DGA amide of Decanoic acid 158948-13-1TSCA 99-358 DGA amide of Castor-oil Fatty acid 212335-58-5

Testing Req’d.* 99-354 DGA amide of Tall Oil Fatty acid 213702-37-5Testing Req’d.* 99-355 DGA amide of Octadecanoic acid 32425-87-9Testing Req’d.* 99-356 DGA amide of Isooctadecanoic acid 212335-61-0Testing Req’d.* 99-357 DGA amide of Soya Fatty acid 212335-57-4


TSCA 99-544 DGA® salt of Tall Oil Fatty acid 216593-48-5TSCA 99-545 DGA salt of Octadecanoic acid 216583-60-7TSCA 99-546 DGA salt of Isooctadecanoic acid 216583-91-4TSCA 99-547 DGA salt of Soya Fatty acid 216593-49-6TSCA 99-548 DGA salt of Castor-oil Fatty acid 216593-54-3TSCA 99-583 DGA salt of Coco Fatty acid 216593-55-4TSCA 99-584 DGA salt of Dodecanoic acid 78543-39-2TSCA 99-585 DGA salt of Neodecanoic acid 216853-95-8TSCA 99-586 DGA salt of Decanoic acid 216583-94-7TSCA 99-587 DGA salt of Nonanoic acid 216583-66-3TSCA 99-588 DGA salt of Boric acid 124756-59-8 TSCA 01-308 DGA salt of Dodecanedioic acid 292601-80-0TSCA 01-309 DGA salt of Undecanedioic acid 292601-81-1TSCA 01-310 DGA salt of Decanedioic acid 292601-82-2TSCA 01-307 DGA salt of CORFREE® M1 acid 292849-36-6TSCA 01-311 DGA salt of 3,5,5-

Trimethyl-hexanoic acid 292601-83-3

Registrations for Derivativesof DGA® Agent continued…


Cobalt Leaching by Commonly Used Metalworking Amines

water

DGA® agentAMP

XTA-771

BHEMATEA

DEAMEA

MIPADIPA

pH = 8.5pH = 9.0

pH = 9.5

0

100

200

300

400

500

600

700

800

900

1000

Dis

solv

ed C

obal

t (pp

m)

Amine

pH = 8.5

pH = 9.0pH = 9.5


Copper Leaching by Commonly Used Metalworking Amines

water blank

DGA® agentAMP

XTA-771

BHEMATEA

MEADEA

MIPADIPA

0

20

40

60

80

100

120

140

160

Dis

solv

ed C

oppe

r (pp

m)

Amines

pH not adjustedpH = 9.0


Copper Corrosion/Leaching

Aqueous solutions of amines and amine-based additives can contribute to copper corrosion/leaching

1% aqueous amine solutions (pH adjusted to desired level with acetic acid) are being tested using a modified ASTM D130 test.

Copper coupons (3 x 1/2 x 1/16 inch) are submerged in the test solutionTest time = 24 hoursTest temperature = 40°C

Dissolved copper is monitored by ICP


Aluminum Staining/Corrosion

Tests include aluminum wrought alloys 2024, 6061 and 7075 and cast alloy 390

Test procedure:Aluminum coupons (1 x 3 x 1/16 in.) are partially submerged in the test solution inside a closed jar. Test solution = 2.5 wt% aqueous amine, the pH of each solution is adjusted to the desired level by adding acetic acidTest temperature = ambientTest time = as listed

Corrosion is documented by weighing the test coupons before and after test; dissolved Al in solution is measured by ICP



Amine Dissolved Al (ppm) Al 7075 Al 6061 Al 2024 Al 390 DGA® agent 5 5.5 7.6 9 AMP 9 7.9 12 11.5 TEA 155 195 235 215 XTA-771 11 9.3 14 14 BHEMA 7.2 4.8 8.6 9 DEA 7.9 9.3 10 11 MEA 10 Blank <1 <1 <1 <1

Test conditions: 2.5 wt% aqueous solution of amine,

test time = 24 hours, pH = 8.8


DGA® agent AMP TEA JEFFOX® A-150 amine

BHEMA DEA Blank

2.5 wt% aqueous solution of amine, test coupon = Al 6061,

test time = 24 hours, pH = 8.8




DGA® agent AMP TEA JEFFOX® A-150 amine

BHEMA DEA Blank

2.5 wt% aqueous solution of amine, test coupon = Al 6061, test time = 88 hours, pH = 8.0



Dissolved Al (ppm) Amine: Isononanoic

acid salt Al 7075 Al 6061 Al 2024 Al 390

DGA® agent 2.6 3.4 5 3.9 AMP 3.6 3.4 3.7 2.2 TEA 10 30 3.7 2.2 XTA-771 3.0 2.6 2.7 2.2 BHEMA 2.2 3.0 <1 <1 DEA 2.5 <1 1.2 <1 MEA 1.9 <1 2.6 <1 Blank 4.1 <1 6.7 6.0

Test conditions: 2.5 wt% aqueous solution of salt (1:1), test time = 24 hours, pH = 8.8 (adjusted with KOH. pH of blank was also adjusted.)


Aluminum Staining/CorrosionDGA® agent AMP TEA JEFFOX® A-150 amine

BHEMA DEA MEA Blank 2.5 wt% aqueous solution of amine-

isononanoic acid salt, test coupon = Al 6061, test time = 24 hours,

pH = 8.8



Test conditions: Aqueous solution 0.1 molar in amine and 0.083 molar in isononanoic acid, test time = 24 hours, pH = 8.8 (adjusted with KOH. pH of blank was also adjusted.)

Dissolved Al (ppm) Amine: Isononanoic

acid salt Al 7075 Al 6061 Al 2024 Al 390

DGA® agent 3.1 3.8 2.8 1.3 AMP 4.7 5.5 3.6 4.5 TEA 40 39 34 32 XTA-771 3.3 4.8 3.7 4.0 BHEMA 1.6 2.2 1.4 1.8 DEA 2.5 3.8 1.2 2.7 MEA 2.7 4.2 2.6 2.7 Blank 2.3 4.0 1.8 2.5


Aluminum Staining/Corrosion Summary of Results

Aluminum staining is pH dependent

Aluminum staining/corrosion is also dependent on the presence of other common additives (such as fatty acids)

Tests run at pH = 8 suggest that DGA® agent may provide an advantage over other amines

Solutions of TEA showed much more significant staining/corrosion than any of the other amines tested.


BHEMA Development

Starting to gain ground in Europe for TEA replacement

Reserve alkalinity curves indicate that BHEMA is slightly stronger than TEA


Benefits of BHEMA

BHEMA is a tertiary amine which can be useful as an alternative to TEA BHEMA has low acute toxicity, low nitrosamine potential, and low volatilityBHEMA is not classified as corrosive under DOTBHEMA showed a lower tendency to stain aluminum than TEACurrently few TSCA registrations

PMNs for TOFA, Decanoic, Neodecanoic, Dodecanedioic, Isononanoic acid salts


3

4

5

6

7

8

9

10

0 20 40 60 80 100mL o f 5% amine so lut io n

DGA(R) Agent

MEAAMP

BHEMATEA

Titration Curves of Metalworking Amines with Decanoic Acid

50g of a 5% decanoic acid solution with various amines


Titration Curves of Metalworking Amines with CORFREE® M1 Acid

3

4

5

6

7

8

9

10

11

0 20 40 60 80 100 120 140

mL of 5% amine solution

pH DGA(R) Agent

MEA

AMP

TEA

BHEMA

50 g of a 5% CORFREE acid solution with various amines

CORFREE® is a registered trademark

of Invista North America


Titration Curves of Metalworking Amines with Isononaoic Acid

3

4

5

6

7

8

9

10

11

0 20 40 60 80 100 120 140 160

mL of 5% amine solution

pH TEA

DGA(R) AgentMEA

AMPBHEMA

50g of a 5% acid solution with various amines


JEFFAMINE® D-2000 Amine

Widely known product similar to other JEFFAMINE etheramines

Acts as a defoamer in metalworking formulations

Fatty acid amides of D-2000 may even be better


Foam Performance of JEFFAMINE® D-2000 Amine

Hydrophobic amine gives defoaming performance in semi-synthetic, but especially synthetic formulations

Amine end groups give enhanced compatibility in formulations

Suggested starting point in a formulation is 0.5-1%

Test Conditions :0.1% sodium dodecylbenzene sulfonateDI WaterPumping at 10 PSI0.02-0.05% add


0

5

10

15

20

25

0 5 10 15 20 25 30 35

Minutes

Foam

Hei

ght

cm

Pumping stopped defoamer added

Blank


Defoamer Performance


Defoamer Performance

0

5

10

15

20

25

0 2 4 6 8 10 12 14

Time, minutes

Foam

Hei

ght,

cm

Defoamer added, pumping stopped

Pumping restarted



New Amines

SURFONAMINE® MW-781 amineVery low molecular weight (131 g/mol)Strong Primary Amine (7.6 meq/g total amine)Has surfactant properties - coupling agent/solubilizerSalts tend to be low foaming CAS# 16499-88-0TSCA, NDSL, EINECS registrations


1% equimolar acid:amine salt in hard water plus 0.1% foaming agent

-5

0

5

10

15

20

25

30

35

40

45

0 5 10 15 20 25

Time, minutes

Foam

Hei

ght,

cm

TEA+Boric acid

MEA+Boric Acid

MW-781+Boric acid

TEA+CORFREE M1 acid

MEA+CORFREE M1 acid

DGA® agent+CORFREEM1 acidMW-781+CORFREE M1acidFoam Blank

MW-781 + CORFREE M1 acid

MW-781+ BORIC ACID

SURFONAMINE® MW-781 Amine Dynamic Foam Test


SURFONAMINE® MW-781 Amine Program

Likely - Vapor phase CI

Multipurpose additive for synthetic and semisyntheticformulations

Excellent candidate for Borate production

Evaluation for a pH “kick”


SURFONAMINE® MW-781 Amine Properties

Water white liquidMelt Point -47°CViscosity 2 cStSpecific Gravity, 0.85

20/20°CTypical assay 99.5% by GC


SURFONAMINE® MW-781 Amine Physical Properties

0

0.5

1

1.5

2

2.5

0 20 40 60 80 100 120Temperature, °C

Visc

osity

, cSt

0.77

0.78

0.79

0.8

0.81

0.82

0.83

0.84

0.85

0.86

Den

sity

, g/c

cDensity

Viscosity


Technical Info

Huntsman Metalworking Chemicals product information (also available on cd)

Web Site: www.huntsman.com/metalworking

Technical: 281-719-7780

DIGLYCOLAMINE JEFFAMINE, SURFONIC, JEFFOX and SURFONAMINE are registered

trademarks of Huntsman Corporation or an affiliate thereof in one or more, but not all, countries.

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