TSE

INDUSTRIES
Volume 8, Issue 1

Technical Information for Performance Solutions

Introducing: Millathane 6010*
Millathane 6010 is a new isocyanate-curable millable polyurethane rubber developed primarily for high-hardness applications such as clay tile die molds. Compounds have excellent strength properties and abrasion resistance.

August 2012

Product Description
Chemical Composition Mooney Viscosity Specific Gravity Appearance Package size/carton Storage stability

Topics:
Millathane 6010* Product Description Processing & Vulcanization Properties Applications Compounding Summary

Polyester millable polyurethane ML(1+4)/100C: 20-40 typical Approximately 1.17 Off white to light beige chunks or blocks 50 pound (22.7 kg) cartons 2 years from date of manufacture (stored under dry and cool conditions)

Millathane 6010 is typically mixed on rubber mills, with stearic acid added with the polymer at the very beginning of the mix to prevent mill sticking. Mills should be kept cool to minimize mill sticking. Internal (e.g., Banbury) mixing is not normally recommended due to the heat buildup of millable urethanes and the potential for sticking and premature vulcanization (scorching). After mixing, compounds should be slabbed off and allowed to air-cool. Mixed compounds have very limited shelf life (storage stability) because of the isocyanate (Thanecure T9/HQEE) cure system) and must be used within 1-2 days of mixing. Storage life can be extended by storing the compound at low temperatures, -5C to +5C. Molded articles are typically produced via compression molding at temperatures of 130 140C for 15 25 minutes, with thick articles taking correspondingly longer times. A postcure of about 8 hours at 80C may improve physical properties and compression set somewhat. Mold shrinkage of cured compounds is typically about 2%.

Processing and Vulcanization

Properties

Vulcanizates based on Millathane 6010 can be produced in hardnesses of 70 to 98 Shore A (up to about 60 Shore D) and offer excellent abrasion resistance, tensile and tear strengths and high elongation at break. Compounds also have good resilience characteristics. Being an ester urethane, Millathane 6010 gives compounds with excellent oil resistance.

Applications
Millathane 6010 is used in high hardness applications that require excellent strength properties and abrasion resistance, such as ceramic tile molds and other technical articles.

Compounding

Millathane 6010 compounds typically contain only the following ingredients: process aid, Thanecure T9, HQEE and an accelerator. Process Aids: Stearic acid is typically used at 0.3 0.5 phr. For additional mill release or to improve mold release, a low molecular weight polyethylene such as AC1702 can be added at 1-2 phr.
*Previously known as Millathane XP7306

The recommendations for the use of our products are based on tests believed to be reliable. However, we do not guarantee the results to be obtained by others under different conditions. Nothing in this literature is intended as a recommendation to use our products so as to infringe on any patent. Millathane and Thanecure are registered trademarks of TSE Industries, Inc.

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TIPS
Thanecure T9 (Superfine), dimerized TDI, is the primary crosslinking agent for Millathane 6010, with HQEE added as a co-crosslinking agent, along with additional Thanecure T9, to achieve higher hardnesses. The chart below shows approximate levels of Thanecure T9 and HQEE to achieve various hardnesses. All formulas shown contain 0.3 phr of ZDMC. The approximate amount of HQEE needed for reaction with Thanecure T9 can be calculated from the formula: HQEE = (T98)*0.57

MILLATHANE FACTOID: Tom Jablonowski will present a paper at the upcoming Rubber Division, ACS meeting in Cincinnati, OH October 9-11: Millathane HS11: A New Millable polyurethane Rubber. Millathane HS11 gives the oil and heat resistance of a polyester urethane with the water and hydrolysis resistance of a polyether urethane.

For applications where a perfect surface finish is critically important, Thanecure T9 and HQEE are often sieved through fine mesh screens (e.g., 200 mesh) before mixing. HQEE should be stored in sealed containers, as it may tend to absorb moisture from the air and give poorer dispersion and properties. Drying in an oven, a vacuum oven if possible, for about 16 - 20 hours at 80C should drive off any moisture that the HQEE has picked up. Accelerators: Dithiocarbamate accelerators such as Bismate (BiDMC), Methazate (ZDMC) or Methyl Ledate (PbDMC) are effective in Millathane 6010 and used at levels of 0.3 0.5 phr. Lead oxides may also be effective as accelerators. A comparison of Bismate, Methazate and Methyl Ledate shows that Bismate functions as well as Methyl Ledate, which has been used for many years with this cure system, and is less hazardous than both materials. It should be noted that Bismate is yellow and will tend to make cured compounds yellowish in color. A small amount of titanium dioxide added to the formula will minimize any yellowish color.

Millathane 6010 Stearic acid Thanecure T9 HQEE Methazate (ZDMC) Methyl Ledate (PbDMC) Bismate (BiDMC) Rheometer, MDR at 135C ts1, min. tc90, min

100 0.3 25 10 0.3

100 0.3 25 10 0.3

100 0.3 25 10

0.3

0.6 5.3

0.5 3.5

0.5 3.2

TIPS V8-1: Millathane 6010

TIPS
Accelerators, continued ZDMC
Physical Properties, Press Cured 20 min./135C Hardness, Shore A 90 Hardness, Shore D 37 TSE-100*, psi 815 MPa 5.6 TSE-300, psi 1180 MPa 8.1 Tensile Strength, psi 3350 MPa 23.1 Elongation, % 720 Tear, Die C, lb/in 403 k N/m 70.5 Tear, Die B, lb/in 384 k N/m 67.2
*TSE-xxx=Tensile Stress at xxx% Elongation

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PbDMC
91 42 965 6.7 1670 11.5 4160 28.7 530 409 71.6 439 76.8

BiDMC
92 42 875 6.0 1280 8.8 4130 28.5 690 464 81.2 440 77.0
MILLATHANE FACTOID: The isocyanate cure system, with Thanecure T9 and HQEE, can also be used in some other Millathane grades like Millathane 26. Contact us for more info.

DIN Abrasion, mm loss Bashore Resilience, % Compression Set, 22 hr/70C, %

47 40 42

35 38 25

38 42 38

Typical Formulations

The typical formulas below span the hardness range from 72 to 98 Shore A, 21 to 57 Shore D. The highest hardness compounds have outstanding tear strength along with the excellent tensile strength and elongation that all the compounds have.
Millathane 6010 Stearic acid Thanecure T9 HQEE Methazate (ZDMC) 100 0.3 8 0 0.3 100 0.3 20 7 0.3 100 0.3 30 13 0.3 100 0.3 40 20 0.3
MILLATHANE FACTOID: The

Physical Properties, Press Cured 20 min./135C Hardness, Shore A 72 Hardness, Shore D 21 TSE-100*, psi 400 MPa 2.8 TSE-200, psi 540 MPa 3.7 TSE-300, psi 655 MPa 4.5 Tensile Strength, psi 2030 MPa 14.0 Elongation, % 870 Tear, Die C, lb/in 337 k N/m 59.0 Tear, Die B, lb/in 363 k N/m 63.5
*TSE-xxx=Tensile Stress at xxx% Elongation

90 34 840 5.8 1060 7.3 1320 9.1 4080 28.1 615 423 74.0 407 71.2

97 50 1425 9.8 1740 12.0 2180 15.0 3820 26.3 470 506 88.6 604 105.7

98 57 1970 13.6 2330 16.1 2910 20.1 3980 27.4 400 551 96.4 758 132.7

hydrolysis resistance of carbon black reinforced compounds will generally be better than non-black compounds.

DIN Abrasion, mm loss Bashore Resilience, % Compression Set, 22 hr/70C, %

40 45 40

35 37 30

46 42 31

61 48 43

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TIPS TSE INDUSTRIES

4370 112th Terrace North Clearwater, FL , USA 33762-4902

www.tse-industries.com

Toll Free: Phone: Fax: E-mail: Internet:

Technology / Service / Experience

800-237-7634 727-573-7676 727-572-0487 millathaneinfo@tse-industries.com www.tse-industries.com

We are here to serve you: Tom Jablonowski, Technical Service Manager Nina Manee, Sales & Marketing Representative Massimo Cerboni, Global Business Director tom.jablonowski@tse-industries.com nina.manee@tse-industries.com massimo.cerboni@tse-industries.com

An ISO 9001:2000 Certified Company

Summary: The new polymer Millathane 6010 gives excellent properties in high hardness compounds, and is an excellent choice for demanding applications.

Ingredients Bismate HQEE Methazate Methyl Ledate Thanecure T9 (Superfine)

Description Bismuth dimethyldithiocarbamate (BiDMC) Hydroquinone Bis(2-hydroxyethyl) Ether Zinc dimethyldithiocarbamate (ZDMC) Lead dimethyldithiocarbamate (PbDMC) TDI Dimer (Dimeric 2.4-toluene diisocyanate)

Supplier/Manufacturer R.T. Vanderbilt Safic-Alcan Chemtura R.T. Vanderbilt TSE Industries, Inc.

Bismate and Methyl Ledate are registered trademarks of R.T. Vanderbilt; Methazate is a registered trademark of Chemtura; Thanecure and Millathane are registered trademarks of TSE Industries, Inc. Ref: XP7504_20120820