Huntsman Products for the Metalworking Industry 2005
Agenda Huntsman Corporation overview Huntsman metalworking specialties and research activities Surfactant Innovations SURFONIC MW-100 additive Low Foam surfactants DGA agent new registrations BHEMA TEA replacement Aluminum and Magnesium studies SURFONAMINE MW-781 butoxypropyl amine JEFFAMINE D-2000 defoamer
Huntsman Business Divisions Advanced Materials Polyurethanes Performance Products Pigments Polymers Base Chemicals Ethylene Design & Composites Engineering Rigids Performance Specialties Polyethylene Propylene Power & Electronics Coatings, Construction & Adhesives Flexibles Elastomers TPU Performance Intermediates Maleic Anhydride & Licensing Titanium Dioxide Polypropylene APAO EPS Butadiene Cyclohexane Paraxylene MTBE
Extensive Global Reach Major Integrated Manufacturing Sites And Technical Centers Close to the Customer
SURFONIC MW-100 Additive A versatile emulsifier for vegetable oils: Inherently low foaming Compatible with phosphate esters for EP Can be used to formulate macro or micro emulsions that are very stable Low pour point (- 2 C) for easy handling Low toxicity
SURFONIC MW-100 Additive Emulsion Characteristics Macro Micro Emulsion Particle size of Microemulsion and Diluted Macroemulsion
Macroemulsion with SURFONIC MW-100 Additive Water 99.00 Falex Wear Test Conditions: 5 minutes conditioning 15 minutes, 675 lbs direct load 8 5 7 0.70 0.30 7 5 8 10 3 MW-100 11.30 88.00 11.70 Soybean oil
SURFONIC MW-100 Additive Effect of Formulation on Torque @ 4000 PSI Soybean Oil Based
Soybean Oil Microemulsion with SURFONIC MW-100 Additive 100 Soybean Oil Microemulsion 0 0 Phosphate ester 100 MW 100 0 Phosphate ester 100
Vegetable Oil-Based Soluble Oil SURFONIC MW-100 20 Emulsifier additive Canola Oil 70 Lubricity agent Sulfurized fatty acid 4 EP agent Alkanolamide 3 Corrosion control Biocide 2 Other 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 -PO Foaming Increasing Component 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) NPE LAE Branched Alcohol Alcohol EO/PO Fatty acid ethoxylates SO, SS SURFONIC N surfactants SURFONIC L surfactants SURFONIC DA and TDA surfactants SURFONIC P and JL surfactants SURFONIC E400-MO surfactant Low Foamers SURFONIC LF surfactants SURFONIC POA surfactants SO SS SY CL LF-18, LF-17, LF-47 POA-L101, POA-17R2, POA-25R2
Lubricity actives for synthetics SY, CL SURFONIC POA-17R2, POA-25R2, POA-L101 and POA-L61 surfactants SURFONIC LF-18 surfactant SURFONIC L4-29X surfactant Coupling agents SO, SS, SY Propylene Glycol Dipropylene Glycol SURFONIC L24-2 and L12-3 surfactants
Extreme Pressure Agents SS, SY Phosphate esters - SURFONIC PE-2258, PE-533, PE-BP2 and PE-2188 surfactants Provide anti-weld functionality Lubricity Additives SO, SS, SY, CL Amides PEG Esters - SURFONIC E400-MO surfactant Reduce friction and heat load Alkanolamines for alkalinity control SO, SS, SY, CL MEA, 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)
Huntsman Amines for Metalworking HOCH 2 CH 2 OCH 2 CH 2 NH 2 DIGLYCOLAMINE agent H 2 N CH 2 CH O CH 3 CH 2 CH NH 2 CH 3 x Product x HOCH 2 CH 2 NH 2 MEA JEFFAMINE D-230 amine JEFFAMINE D-400 amine 2-3 5-6 (HOCH 2 CH 2 ) 2 NH DEA (HOCH 2 CH 2 ) 3 N (HOCH 2 CH 2 ) 2 NCH 3 TEA BHEMA CH 2 [OCH 2 CH(CH 3 )]NH 2 x CH 3 CH 2 CH 2 [OCH 2 CH(CH 3 )]NH 2 y CH 2 [OCH 2 CH(CH 3 )]NH 2 z x + y + z = ~5.3 JEFFAMINE T-403 amine (XTA-771)
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 Issues Toxicity Misting and Volatility Registration Issues Performance Issues Reserve Alkalinity ph Stability Corrosion 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 costeffective 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 Derivatives of DGA Agent TSCA 99-350 DGA amide of Neodecanoic acid 212335-62-1 TSCA 99-351 DGA amide of Coco Fatty acid 212335-59-6 TSCA 99-352 DGA amide of Dodecanoic acid 20138-28-7 TSCA 99-353 DGA amide of Decanoic acid 158948-13-1 TSCA 99-358 DGA amide of Castor-oil Fatty acid 212335-58-5 Testing Req d.* 99-354 DGA amide of Tall Oil Fatty acid 213702-37-5 Testing Req d.* 99-355 DGA amide of Octadecanoic acid 32425-87-9 Testing Req d.* 99-356 DGA amide of Isooctadecanoic acid 212335-61-0 Testing Req d.* 99-357 DGA amide of Soya Fatty acid 212335-57-4
Registrations for Derivatives of DGA Agent continued TSCA 99-544 DGA salt of Tall Oil Fatty acid 216593-48-5 TSCA 99-545 DGA salt of Octadecanoic acid 216583-60-7 TSCA 99-546 DGA salt of Isooctadecanoic acid 216583-91-4 TSCA 99-547 DGA salt of Soya Fatty acid 216593-49-6 TSCA 99-548 DGA salt of Castor-oil Fatty acid 216593-54-3 TSCA 99-583 DGA salt of Coco Fatty acid 216593-55-4 TSCA 99-584 DGA salt of Dodecanoic acid 78543-39-2 TSCA 99-585 DGA salt of Neodecanoic acid 216853-95-8 TSCA 99-586 DGA salt of Decanoic acid 216583-94-7 TSCA 99-587 DGA salt of Nonanoic acid 216583-66-3 TSCA 99-588 DGA salt of Boric acid 124756-59-8 TSCA 01-308 DGA salt of Dodecanedioic acid 292601-80-0 TSCA 01-309 DGA salt of Undecanedioic acid 292601-81-1 TSCA 01-310 DGA salt of Decanedioic acid 292601-82-2 TSCA 01-307 DGA salt of CORFREE M1 acid 292849-36-6 TSCA 01-311 DGA salt of 3,5,5- Trimethyl-hexanoic acid 292601-83-3
Cobalt Leaching by Commonly Used Metalworking Amines 1000 900 Dissolved Cobalt (ppm) 800 700 600 500 400 300 200 100 ph = 8.5 ph = 9.0 ph = 9.5 0 water DGA agent AMP XTA-771 BHEMA TEA DEA MEA MIPA DIPA ph = 8.5 ph = 9.0 ph = 9.5 Amine
Copper Leaching by Commonly Used Metalworking Amines DIPA 160 140 120 100 80 60 40 20 Dissolved Copper (ppm) 0 water blank DGA agent AMP XTA-771 BHEMA TEA MEA DEA MIPA Amines ph not adjusted ph = 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 solution Test time = 24 hours Test 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 acid Test temperature = ambient Test time = as listed Corrosion is documented by weighing the test coupons before and after test; dissolved Al in solution is measured by ICP
Aluminum Staining/Corrosion 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
Aluminum Staining/Corrosion 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
Aluminum Staining/Corrosion 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
Aluminum Staining/Corrosion Amine: Dissolved Al (ppm) 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/Corrosion DGA agent AMP TEA JEFFOX A-150 amine BHEMA DEA MEA Blank 2.5 wt% aqueous solution of amineisononanoic acid salt, test coupon = Al 6061, test time = 24 hours, ph = 8.8
Aluminum Staining/Corrosion Amine: Dissolved Al (ppm) 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 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.)
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 volatility BHEMA is not classified as corrosive under DOT BHEMA showed a lower tendency to stain aluminum than TEA Currently few TSCA registrations PMNs for TOFA, Decanoic, Neodecanoic, Dodecanedioic, Isononanoic acid salts
Titration Curves of Metalworking Amines with Decanoic Acid 50g of a 5% decanoic acid solution with various amines 10 9 8 7 6 5 4 3 DGA(R) Agent MEA AMP BHEMA TEA 0 20 40 60 80 100 ml of 5% amine solution
Titration Curves of Metalworking Amines with CORFREE M1 Acid 50 g of a 5% CORFREE acid solution with various amines 11 10 9 8 ph 7 6 5 4 DGA(R) Agent MEA AMP TEA BHEMA 3 0 20 40 60 80 100 120 140 CORFREE is a registered trademark of Invista North America ml of 5% amine solution
Titration Curves of Metalworking Amines with Isononaoic Acid 11 10 9 8 50g of a 5% acid solution with various amines ph 7 6 5 4 3 TEA DGA(R) Agent MEA AMP BHEMA 0 20 40 60 80 100 120 140 160 ml of 5% amine solution
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 semisynthetic, 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 sulfonate DI Water Pumping at 10 PSI 0.02-0.05% add
JEFFAMINE D-2000 Amine Defoamer Performance 25 Pumping stopped defoamer added 20 Foam Height cm 15 10 Blank 5 0 0 5 10 15 20 25 30 35 Minutes
JEFFAMINE D-2000 Amine Defoamer Performance 25 20 Defoamer added, pumping stopped Foam Height, cm 15 10 5 0 Pumping restarted 0 2 4 6 8 10 12 14 Time, minutes
New Amines SURFONAMINE MW-781 amine Very low molecular weight (131 g/mol) Strong Primary Amine (7.6 meq/g total amine) Has surfactant properties - coupling agent/solubilizer Salts tend to be low foaming CAS# 16499-88-0 TSCA, NDSL, EINECS registrations
SURFONAMINE MW-781 Amine Dynamic Foam Test 45 40 35 1% equimolar acid:amine salt in hard water plus 0.1% foaming agent TEA+Boric acid MEA+Boric Acid MW-781+Boric acid TEA+CORFREE M1 acid MEA+CORFREE M1 acid Foam Height, cm 30 25 20 15 10 MW-781 + CORFREE M1 acid DGA agent+corfree M1 acid MW-781+CORFREE M1 acid Foam Blank 5 0-5 MW-781+ BORIC ACID 0 5 10 15 20 25 Time, minutes
SURFONAMINE MW-781 Amine Program Likely - Vapor phase CI Multipurpose additive for synthetic and semisynthetic formulations Excellent candidate for Borate production Evaluation for a ph kick
SURFONAMINE MW-781 Amine Properties Water white liquid Melt Point -47 C Viscosity 2 cst Specific Gravity, 0.85 20/20 C Typical assay 99.5% by GC
SURFONAMINE MW-781 Amine Physical Properties 2.5 0.86 0.85 2 0.84 Viscosity, cst 1.5 1 Viscosity Density 0.83 0.82 0.81 0.8 Density, g/cc 0.5 0.79 0.78 0 0 20 40 60 80 100 120 Temperature, C 0.77
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.