KR20070030776A - NBC-Resistant Composition - Google Patents

Abstract

A composition comprising terpolymers of ethylene-propylene-diene monomers, flame retardants and antibacterial agents.

NBC-resistant, marker sleeve, ethylene-propylene-diene terpolymer, EPDM, flame retardant, hazardous environment

Description

NBC-resistant composition

The present invention relates to a composition for use in a hazardous environment. In particular, the present invention relates to compositions that exhibit elastomeric properties and are resistant to harmful environments containing nuclear, biological or chemical substances.

Articles used in hazardous environments can be subjected to various destructive materials, such as nuclear, biological and chemical (NBC) materials. Such environments typically appear in military applications, and war can expose such items to various NBC materials. Other applications may include industrial processes, chemical plants, nuclear reactors, and biohazardous industries. Articles used in these applications must be NBC resistant to provide continued use over a long period of time despite exposure to NBC material.

Nuclear materials generally include radiation and heat release, such as emission from nuclear reactions or exposure to extreme heat and solar conditions. Biological materials generally include biological organisms such as viruses, bacteria and fungi; And biochemicals. Chemical substances generally refer to substances that damage an article through chemical reactions, toxicity enhancement and chemical removal (eg extraction). Common chemicals include solvents, corrosive substances, oxidizing agents and highly toxic organic substances.

NBC material may not only damage the article, but also remove the identification label located on the article. Identification labels are often applied to articles to serve a variety of information purposes. For example, the label may provide information about the product name, manufacturer name, barcode, serial number, batch number and expiration date. To that end, the label is preferably visually readable and durable. However, exposure of an article that is not resistant to such a hazardous environment can damage the article and remove the identification label. As such, there is a need for compositions that are resistant to NBC materials that can be used to make articles that are correspondingly resistant to NBC materials.

Brief summary of the invention

The present invention relates to compositions comprising terpolymers, flame retardants and antibacterial agents of ethylene-propylene-diene monomers (EPDM). The composition is resistant to NBC materials and can be used to make articles for use in hazardous environments containing NBC materials.

The present invention also relates to an article comprising a mixture of terpolymers, flame retardants and antibacterial agents of EPDM. The article also includes a concentrated energy beam-induced marker located on the surface of the article. The marker can provide information for a variety of purposes, is visually readable and durable for use in hazardous environments containing NBC materials.

1 is a perspective view of an article of the present invention for use with a cable.

2 is a perspective view in a relaxed state of the article of the present invention.

3 is a perspective view in an expanded state on the core of the article of the present invention.

4 is another perspective view in the expanded state on the core of the article of the present invention.

5 is a perspective view in the expanded state with respect to the cable of the labeled article of the present invention.

6 is a perspective view of an article of the present invention partially located on the core and partially located on the cable.

While the above-mentioned figures describe several embodiments of the present invention, other embodiments are also contemplated, as indicated in the specification. In all cases, this disclosure is shown as representative of the invention and not as a limitation. It should be understood that many other modifications and embodiments can be devised by those skilled in the art, which fall within the spirit and scope of the invention. The drawings may not be drawn in proportion to the dimensions. Like reference numerals have been used throughout the drawings to refer to like parts.

The present invention includes compositions that are resistant to NBC materials, including terpolymers, flame retardants, and antibacterial agents of EPDM. The composition can be used to make articles that are correspondingly NBC resistant for use in a hazardous environment. It is generally desirable for the article to prevent the capture of liquid and aggressive powder materials, such as corrosive materials, highly toxic organic materials and biochemicals. Similarly, the article is preferably resistant to chemical attack, such as exposure to gas and hydraulic fluids and solvents to liquids and vapors. Resistance to such materials reduces or eliminates collapse of the article, thus providing longer product life.

Terpolymers of EPDM, referred to herein as "EPDM rubber", exhibit good resistance to heat, ozone, oxidation, climate and polar solvents. Examples of suitable diene terpolymers used to form EPDM rubbers include ethylene norbornene and dicyclopentadiene. EPDM rubbers also provide elastomeric properties to articles made from the compositions of the present invention. The elastomeric properties expand and contract the article to fit the accompanying elements. For example, the compositions of the present invention are useful for making sleeve articles that can be expanded to fit around cables, wires, and other transport and distribution flows such as fluid hoses or tubes.

Flame retardants provide resistance to heat and flames that may be common in many industrial and military applications. Examples of suitable flame retardants include the following commercially available from Albemarle Corporation, Houston, Texas: decabromodiphenyl oxide (eg, "Saytex 102E"); Tetradecabromodiphenoxy benzene (eg, "Seytex 120"); 1,2-bis (pentabromophenyl) ethane (eg, "Seytex 8010"); 1,2-bis (tetrabromophthalimide) ethane (eg, "Sextex BT-93" and "Sextex BT-93W"); Tetrabromobisphenol A (eg, "Seytex CP-2000"); Hexabromocyclododecane (eg, "Sextex HP-900" and "Sextex 9006L"); Brominated polystyrenes (eg, "Seytex HP-7010 P / G" and "Seytex HP-3010"); And combinations thereof.

In addition to flame retardants, flame retardant synergists may also be incorporated into the compositions of the present invention to assist the flame retardants. Examples of suitable flame retardant synergists include antimony trioxide (available under the trade name "Seytex FS-100" from Alberta), antimony pentoxide and sodium antimonite (Nyacol Nano Technologies, Inc., Ashland, Commercially available under the trade name " Nycol Burn EX ZTA " from Massachusetts) and combinations thereof.

Antimicrobial agents incorporated into the compositions of the present invention are preferably a broad spectrum antimicrobial that provides protection against a wide range of biological materials. Examples of suitable antimicrobial agents include antifungal agents, agicides, antifouling agents, fungicides and combinations thereof. Antifungal and acaricides include substances that prevent fungi, algae, mold, yeast, filamentous fungi, and the like. Examples of suitable antifungal and acaricides include zinc complexes of pyrithione (e.g., 2-pyridinethiol-1-oxide, zinc complexes) (e.g., "Zinc Omadine"), sodium complexes of pyrithione ( Eg, 2-pyridinethiol-1-oxide, sodium salt), (eg "sodium omadine"), iodopropynyl butyl carbamate compound (eg 3-iodopropynylbutyl carbamate), (eg "Omacide IPBC"), and combinations thereof, all of which are commercially available from Arch Chemicals, Inc., Cheshire, Connecticut. Antifouling agents are similar to antifungal and algae and are designed for sea use. Examples of suitable antifouling agents include copper complexes of pyrithione (eg, "Copper Omarin"), which are commercially available from Arc Chemicals. Fungicides are preferred that are effective against both gram positive and gram negative bacteria. Examples of suitable fungicides are hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine and 1,3,5-triazine-1,3,5- (2H, 4H, 6H) Triethanol (eg, "Triadine"), which is commercially available from ARK Chemicals.

All concentrations herein are expressed in weight percentages unless otherwise noted. Suitable component concentrations in the compositions of the present invention comprise from about 10.0% to about 95.5% EPDM rubber, from about 10.0% to about 50.0% flame retardant and from about 0.05% to about 1.0% antimicrobial agent, based on the total composition weight of the composition of the present invention. Range. Particularly suitable component concentrations in the compositions of the present invention are from about 30.0% to about 80.0% EPDM rubber, from about 10.0% to about 30.0% flame retardant and from about 0.1% to about 0.4% antimicrobial agent, based on the total composition weight of the composition of the present invention. Range. For compositions comprising a flame retardant synergist, suitable concentrations of flame retardant synergists in the compositions of the present invention range from about 1.0% to about 10.0% based on the total composition weight of the compositions of the present invention and are flame retardant in the compositions of the present invention. Particularly suitable concentrations of synergists range from about 1.0% to about 4.0%.

The composition of the present invention may also comprise additional materials such as pigments, antioxidants, stabilizers, oils, processing aids, fillers, crosslinking materials and acrylic aids.

Examples of suitable pigments include titanium dioxide; Carbon black; zinc oxide; Depression blue; Cadmium sulfide; Iron oxide; Chromate of lead, zinc, barium and calcium; Azo; Thioindigo; Anthraquinones; Anthrone; Tripenone dioxazine; Fatty dye pigments; Phthalocyanine pigments such as copper phthalocyanine pigments and derivatives thereof; Quinacridone pigments; All are products of Ciba Specialty Chemicals of Tarrytown, NY, trade names "Cinquasia", "Cromophtal", "Filamid", "Filester", "Filofin", "Hornachrome", "Horna molybdate", "Hornatherm", "Irgacolor", "Irgalite", "Irgasperse", "Irgazin", "Micranyl", "Microlen", "Microlith", "Microsol" and Pigments sold under “Unisperse”; And combinations thereof. Suitable concentrations of pigments in the compositions of the present invention include from about 0.1% to about 10.0% based on the total composition weight of the compositions of the present invention, and particularly suitable concentrations of pigments in the compositions of the present invention range from about 1.0% to about 5.0% Include.

Examples of suitable antioxidants are all R.T. Zinc 2-mercaptotolimidazole in petroleum processing oils (e.g., "Vanox ZMTI" and "Vanox MTT"), a product of RT Vanderbilt Company, Inc., Norwalk, Connecticut, and Mixtures of octylated diphenylamines (eg, "Agerite Stalite"); And combinations thereof. Suitable concentrations of antioxidants in the compositions of the present invention range from about 0.1% to about 5.0% based on the total composition weight of the compositions of the present invention, and particularly suitable concentrations of antioxidants in the compositions of the present invention are from about 0.5% About 1.5%.

Examples of suitable oils include hydrocarbon oils, inorganic oils, rosin oils, paraffinic petroleum, oleic acid, glycerol, polypropylene glycol, polybutylene glycol and combinations thereof. Suitable concentrations of oil in the compositions of the present invention range from about 5.0% to about 40.0% based on the total composition weight of the compositions of the present invention, and particularly suitable concentrations of oil in the compositions of the present invention range from about 10.0% to about 25.0% to be.

Examples of suitable processing aids include mixtures of fatty acid metal (eg, zinc) soaps and amides (eg, "Struttol A 50", "stall", available from Struktol Company of America, Stow, Ohio). Lactol A 60 "," Strutol A 61 "," Strutol EF 44 A ", and" Strutol WB 42 "); Mixtures of rubber compatible non-cured fatty acid soaps (eg “Struttol EP 52”); Fatty acid esters and soap-bonded fillers (eg, "Struttol W 34" and "Struttol WB 212"); Mixtures of lubricants and fatty acid derivatives (eg, "Struttol W 80"); Mixtures of esters of fatty acids and zinc soaps (eg, “Structol WA 48”); Mixtures of fatty acid soaps that are predominantly calcium (eg, "Structol WB 16"); Mixtures of aliphatic fatty acid esters and condensation products (eg, “Struttol WB 222”); Condensation products of fatty acid derivatives and silicones (eg, “Struttol WS 180”); Organosilicon compounds on inorganic carriers (eg, “Struttol WS 280”); And combinations thereof. Suitable concentrations of processing aids in the compositions of the present invention range from about 0.1% to about 10.0% based on the total composition weight of the compositions of the present invention, and particularly suitable concentrations of processing aids in the compositions of the present invention are from about 0.5% to about 2.0 Range of%.

Fillers may be incorporated into the compositions of the present invention to improve physical and rheological properties. Examples of suitable fillers include clay fillers, hydrated amorphous silicas, precipitated silicas, fumed silicas, burned silicas, hydrophobized silicas, derivatives thereof and combinations thereof. Examples of suitable clay fillers include the trade names "Translink 37", "Translink 77", "Translink 445", "Translink 555" and "Translink" from Engelhard Corporation, Iselin, New Jersey. Silane-treated kaolin clay (aluminum silicate) fillers available under HF-900 ". Suitable concentrations of the fillers in the compositions of the present invention range from about 1.0% to about 50.0% based on the total composition weight of the compositions of the present invention, and particularly suitable concentrations of the fillers in the compositions of the present invention are about 10.0% to about 25.0 Range of%.

The silane coupling agent helps to bind the filler to the polymer of the composition of the present invention. Examples of suitable silane coupling agents are all vinyl silanes (eg, "A-172 DLC"), methacryl silanes (eg, "A-174 DLC" available from Natrochem, Inc., Savannah, Georgia). "), Amino silanes (eg," A-1100 DLC "and" A-1120 "); Both liquid tetrasulfide silanes (eg, "Silquest A-1289") and liquid disulfide silanes (eg, "Silquest A-" available from the OSI Specialties Division of Witco Corporation, Danbury, Connecticut). 1589 "); And combinations thereof. Suitable concentrations of the silane coupling agent in the compositions of the present invention range from about 0.1% to about 5.0% based on the total composition weight of the composition, and particularly suitable concentrations of silane coupling agents in the composition of the present invention are from about 0.1% In the range of about 1.0%.

Examples of suitable crosslinkers include amines, and R.T. Peroxides such as the following peroxides available from RT Vanderbilt Company, Inc., Norwalk, Connecticut: Dicumyl peroxide (e.g., "Varox DCP", "Varox DCP-40C", "Varox DCP-40KE") And "Varox DCP-40KE-HP"); Benzoyl peroxide (eg, "Varox ANS"); Dibenzoyl peroxide (eg, "Varox A 75"); 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (e.g. "Varox DBPH", "Varox DBPH 40 MB", "Varox DBPH-50", "Varox DBPH-50-HP", "Varox DBPH-P20" and "Varox DCP-40KE"); t-butyl perbenzoate (eg, "Varox TBPB" and "Varox TBPB-50"); 2,5-dimethyl-2,5-di (t-butylperoxy) hexin-3 (eg, "Varox 130" and "Varox 130-XL"); Alpha, alpha-bis (t-butylperoxy) diisopropylbenzene (eg, "Varox VC-R"); Di- (2-t-butylperoxyisopropyl) benzene (eg, "Varox 802-40C", "Varox 802-40KE" and "Varox 802-40KE-HP"); Di- (2-t-butylperoxyisopropyl) benzene in EPR (eg, "Varox 802-40MB"); Derivatives thereof; And combinations thereof. Suitable concentrations of crosslinkers in the compositions of the present invention range from about 0.5% to about 5.0% based on the total composition weight of the compositions of the present invention, and particularly suitable concentrations of crosslinkers in the compositions of the present invention range from about 1.0% to about 3.0% Range.

Acrylic aids may be incorporated into the compositions of the present invention to enhance the crosslinking reaction. Examples of suitable acrylic aids include multi-functional monomers such as bi- and trifunctional monomers. Examples of suitable difunctional monomers include 1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, 1, available from Sartomer Company, Inc., Exton, Pennsylvania. 4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, aliphatic dimethacrylate monomers, alkoxylated aliphatic di Acrylate, alkoxylated cyclohexane dimethanol diacrylate, alkoxylated cyclohexane dimethanol diacrylate, alkoxylated cyclohexane dimethanol diacrylate, alkoxylated hexanediol diacrylate, alkoxylated hexanediol Diacrylate, alkoxylated hexanediol diacrylate, alkoxylated neopentyl glycol diacrylate, alkoxylated neopentyl glycol diacrylate, aromatic dimethac Relative monomers, caprolactone modified neopentylglycol hydroxypivalate diacrylate, caprolactone modified neopentylglycol hydroxypivalate diacrylate, cyclohexane dimethanol diacrylate, cyclohexane dimethanol dimethacryl Ethylene, Diethylene Glycol Diacrylate, Diethylene Glycol Dimethacrylate, Dipropylene Glycol Diacrylate, Ethoxylated (10) Bisphenol Alpha Diacrylate, Ethoxylated (2) Bisphenol Alpha Dimethacrylate, Ethoxy Silylated (3) bisphenol alpha diacrylate, ethoxylated (30) bisphenol alpha diacrylate, ethoxylated (30) bisphenol alpha dimethacrylate, ethoxylated (4) bisphenol alpha diacrylate, ethoxylated (4) bisphenol alpha dimethacrylate, ethoxylated (8) bisphenol alpha dimethacrylate, to Silylated bisphenol alpha dimethacrylate, ethoxylated bisphenol alpha dimethacrylate, ethoxylated (10) bisphenol dimethacrylate, ethoxylated (6) bisphenol alpha dimethacrylate, ethylene glycol dimethacrylate , Hydroxypivalaldehyde modified trimethylolpropane diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, polyethylene glycol (200) diacrylate, polyethylene glycol (400) diacrylate, polyethylene glycol ( 400) Dimethacrylate, Polyethylene Glycol (600) Diacrylate, Polyethylene Glycol (600) Dimethacrylate, Polyethylene Glycol Dimethacrylate, Polypropylene Glycol (400) Dimethacrylate, Propoxylated (2) Neopentyl glycol diacrylate, tetraethylene glycol diacrylate, tetra Styrene glycol dimethacrylate, tricyclodecane dimethanol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tripropylene glycol diacrylate, tripropylene glycol diacrylate and combinations thereof Can be.

Suitable concentrations of acrylic aids in the compositions of the present invention range from about 0.1% to about 5.0% based on the total composition weight of the compositions of the present invention, and particularly suitable concentrations of acrylic aids in the compositions of the present invention are from about 0.5% to about 2.0 Range of%.

The composition of the present invention is a combination of EPDM rubber, flame retardant and antioxidant, and then the components at a temperature of about 141 ° C. at a rate of about 50 revolutions per minute in a 10 D two-wing tangent Banbury mixer with a capacity of 220 liters. It can be prepared by mixing for about 4-8 minutes. The Banbury mixer is commercially available from Farrel Corporation, Ansonia, Connecticut. The mixed composition can then be passed through a 25.4-cm extruder equipped with a 100 mesh sieve to remove undispersed particles.

Additional materials such as pigments, antioxidants, oils, processing aids, neutralizers, rheology modifiers, fillers and silane coupling agents may be added to the EPDM rubber, flame retardants and antioxidants prior to mixing. However, if a crosslinking agent or acrylic aid is to be introduced into the composition, the addition of these components must be done in a second mixing step at lower temperature to prevent premature crosslinking. After combining, mixing and passing the EPDM rubber, flame retardant and antimicrobial agent through a mesh sieve, crosslinkers and acrylic aids can be added and the entire composition is about 45 revolutions / minute in a 10D two-wing tangential Banbury mixer with a capacity of 220 liters. Mixing at a temperature of about 102 ° C. for about 1.5 to 3 minutes.

The compositions of the present invention can be used to make a variety of articles resistant to NBC materials. Suitable articles made from the compositions of the present invention may include marker sleeves, tubes, polymer sheets, protective layers, containers, and the like. The article can be formed by various methods such as single screw, double screw or other extruder systems. Suitable extruders include 5.1-cm single-screw extruders having a length-to-diameter ratio of about 15. Suitable operating conditions for the extruder include an extrusion zone temperature and die temperature of about 80 ° C., and a rotation speed of about 20 to about 40 revolutions per minute. This gives a material flow rate of about 3 to 12 meters / minute. The particular pin and die will tell the inner diameter and layer thickness of the article before crosslinking. Upon exiting the extruder, the article is passed through an autoclave to crosslink the components of the composition to form an article. Suitable autoclave conditions include applying a steam pressure of about 620 kilopascals for about 45 minutes, which corresponds to exposure for about 45 minutes at atmospheric pressure to a temperature of about 166 ° C.

As mentioned above, the elastomeric nature of EPDM rubber allows the article to expand and contract to fit the accompanying elements. As such, the compositions of the present invention are particularly suitable for making inflatable marker sleeves, such as the marker sleeve 10 shown as used on the cable 12 in FIG. 1.

The marker sleeve 10 is a tubular article that provides information about the transmission or dispensing progress, such as electrical and telephone cables, wires, fluid-delivery pipes and conduits. The cable 12 is an example of such a transmission or distribution proceeding, but the marker sleeve 10 can be used for any transmission or distribution proceeding. The marker sleeve 10 may provide information even after exposure to the NBC material.

As shown, the marker sleeve 10 comprises a radial wall 11, an inner surface 14 and an outer surface 16, wherein the inner surface 14 is an outer surface of the cable 12. (18) extend around, face or typically contact with it. Marker 20, which is information labeled by a concentrated energy beam, is located above the outer surface 16. Concentrated energy beams mean focused emissions with the direction of radiation, such as a laser beam. The marker 20 may be one cover or a plurality of signs, and may include various characters (ie, alpha-numeric) or graphic characters, symbols, and the like. The marker 20 may also be or include a machine-readable marker such as a barcode. The marker 20 may be formed by conventional laser labeling techniques, or the marker may be filed under the same designation as the "cold-shrink marker sleeve" of the invention, which is incorporated herein by reference in its entirety. It may be formed by the technique described in the pending patent application (patent document No. 59575US002).

In this selection, the marker 20 inflates the marker sleeve 10 from the relaxed state, marks the outer surface 16 (in the expanded state) with a concentrated energy beam, and the labeled marker sleeve 10 ) To form a low temperature shrinkage in a relaxed state again. The term "cold shrink" herein means that the marker sleeve 10 can be contracted in a relaxed state from an expanded state at a temperature of less than about 50 ° C. When the marker sleeve 10 is cold contracted towards the relaxed state, the marker 20 retains a high level of visual readability. In addition, the marker sleeve 10 can be used in a hazardous environment containing NBC material, so that the marker 20 retains a substantially high level of visual readability.

Although shown as a single tubular article in FIG. 1, the marker sleeve 10 of the present invention may include various shaped features, such as tubular articles having multiple branches (ie, multiple inlets and outlets). The mark 20 on the marker sleeve 10, which is a tubular article with multiple branches, can be formed by separately inflating, marking and cold shrinking each branch portion.

The composition of the present invention may further comprise an energy beam absorber, such as a laser beam absorber. Suitable energy beam absorbers are disclosed in the same-pending pending patent application (patent document No. 59575US002), entitled "Low Temperature-Shrink Marker Sleeve". Suitable concentrations of the energy beam absorber in the composition of the present invention include from about 0.01% to about 5.0% of the energy beam absorber based on the total composition weight of the composition. Particularly suitable concentrations of the energy beam absorber in the composition of the present invention include from about 0.01% to about 3.0% of the energy beam absorber based on the total composition weight of the composition.

EPDM rubber exhibiting elastomeric properties allows the marker sleeve 10 to expand from its relaxed state to an expanded state without rupture or cracking, and also to allow the marker sleeve 10 to be relaxed from the expanded state again. Allow for low temperature shrinkage. The pigment generally provides the base color to the marker sleeve 10, including the base color of the outer surface 16. Similarly, when heated by a concentrated energy beam, the energy beam absorber generally provides a complementary color to the marker 20. For high visual readability of the mark 20, it is desirable to use pigments and energy beam absorbers that provide a high contrast between the base color of the outer surface 16 and the contrasting color of the mark 20. For example, light yellow or white may be suitable for the outer surface 16 when the energy beam absorber provides a dark gray or black color for the mark 20. Otherwise, if the energy beam absorber provides a bright color for the marker 20, a dark color may be suitable for the outer surface 16. In either case, high color contrast between the base color and the contrasting color increases the visual legibility of the marker 20.

In order to form the marker sleeve 10 with the marker 20 located on the outer surface 16, the composition of the present invention is mixed, extruded and crosslinked as described below to form a marker sleeve as shown in FIG. 10) to provide. 2 is a perspective view of the marker sleeve 10 in its relaxed state prior to inflation and labeling. When the marker sleeve 10 is in a relaxed state, the radial wall 11 has a longitudinal length (A), an inner diameter (B), an outer diameter (C) and a layer thickness (D). The longitudinal length (A) and inner diameter (B) will vary based on individual needs, such as the dimensions of the cable 12. The inner diameter B is preferably suitable for exhibiting a seam fit around the surface 18 of the cable 12 to at least prevent the marker sleeve 10 from slipping along the cable 12.

The outer diameter (C) is generally determined by the inner diameter (B) and the layer thickness (D), wherein the layer thickness (D) is substantially uniform around and along the marker sleeve 10. The layer thickness (D) is thin enough so that the marker sleeve 10 can be easily inflated from the relaxed state, but also when the marker sleeve 10 is in the inflated state, the laser marker is placed on the marker sleeve 10. It is preferred that it is thick enough so as not to burn through the radial wall 11. Suitable layer thicknesses (D) of the marker sleeve 10 in the relaxed state range from about 0.76 millimeters (mm) (30 mils) to about 2.29 mm (90 mils). A particularly suitable layer thickness D of the marker sleeve 10 in the relaxed state ranges from about 1.27 mm (50 mils) to about 1.78 mm (70 mils).

After the marker sleeve 10 is formed, the marker sleeve 10 is expanded in cross-sectional area from the relaxed state to the expanded state. The terms "expanded", "expansion", "expanded state" and the like herein refer to cross-sectional expansion that increases the inner diameter (B) and outer diameter (C), in contrast to the longitudinal expansion that increases the longitudinal length (A). it means. Referring to FIG. 3, which shows the marker sleeve of FIG. 2 inflated about the core 22, the marker sleeve 10 can be inflated and positioned on the core 22 in any conventional manner. The core 22 may be any kind of rigid device for holding the marker sleeve 10 in an expanded state, such as a rigid hollow plastic tube. When the marker sleeve 10 is in an inflated state as shown in FIG. 3, the radial wall 11 has a longitudinal length A ′, an inner diameter B ′, an outer diameter C ′ and a layer thickness ( D '). Due to expansion, inner diameter B 'and outer diameter C' are larger than inner diameter B and outer diameter C, respectively. The degree of diameter increase from B to B 'and from C to C' depends on the extent to which the marker sleeve 10 is inflated. Suitable expansion of the marker sleeve 10 generally includes an increase from the inner diameter B to the inner diameter B 'in the range of about 150% to about 300%. Particularly suitable inflation ranges of the marker sleeve 10 include an increase from the inner diameter B to the inner diameter B 'in the range of about 200% to about 250%.

The expansion of the marker sleeve 10 also makes the layer thickness D 'thinner than the layer thickness D. FIG. The degree of difference between the layer thickness D and the layer thickness D 'depends on the specific composition of the marker sleeve 10 and the extent to which the marker sleeve 10 expands. As already discussed, the layer thickness D 'of the marker sleeve 10 in the expanded state must be thick enough so that the laser marker is not completely burned through the radial wall 11 of the marker sleeve 10. The expansion of the marker sleeve 10 also typically causes the longitudinal length A 'of the inflated marker sleeve 10 to be shorter than the longitudinal length A of the marker sleeve 10 in a relaxed state.

4 is a perspective view of the marker sleeve 10 in the inflated state and on the core 22 after the outer surface 16 has been labeled to form the marker 20. While the marker sleeve 10 is in the inflated state, the marking on the outer surface 16 increases the surface area of the labeled portion of the outer surface 16. As such, a larger mark 20 can be formed. The size difference of the marker 20 is best seen by comparing the marker 20 shown in FIGS. 1 and 4. The marker 20 shown in FIG. 4 with the marker sleeve 10 inflated is in the circumferential direction of the marker sleeve 10 than the marker 20 shown in FIG. 1 with the marker sleeve 10 relaxed. Longer, narrower print surface height. Laser labeling the marker sleeve 10 in a relaxed state will increase the accuracy and consistency required to make the visually readable markings. As such, inflating the marker sleeve 10 prior to the labeling allows for the formation of a marker 20 that exhibits a higher degree of detail and resolution, and thus is very much when the marker sleeve 10 is in a relaxed state. Reduce the precision of the markers needed to produce an easy-to-read marker 20.

The mark 20 is formed by marking the outer surface 16 of the marker sleeve 10 with a concentrated energy beam, such as a laser beam. In one embodiment, the marker 20 is external surface 16 of the marker sleeve 10 to laser generated radiation (ie, a laser beam) at an energy level sufficient to burn a selected portion of the external surface 16. It can be formed by exposing. Burning occurs when the heat of the concentrated energy beam is transferred from the energy beam absorber to initiate the chemical reaction of the polymer. The chemical reaction changes the color of the outer surface 16 at the burning position, which creates a dark contrast marker that visually contrasts with the remaining lighter primary color portion of the outer surface 16.

Otherwise, in a second embodiment, different laser beam adjustments can be used to foam the outer surface 16 during the formation of the marker 20. This is useful for making light-colored marks on the outer surface 16. As mentioned above, the foaming is also effected by the chemical reaction of the polymer upon heating with a concentrated energy beam. However, the chemical reaction produces a light colored label at the foaming position, which is visually contrasted with the remaining dark colored portion of the outer surface 16. In either embodiment, the concentrated energy beam is moved around the outer surface 16 as needed to make the markings 20 of the desired letters, figures, symbols and the like.

An example of a suitable laser system for making such a mark on the outer surface 16 of the radial wall 11 is an Nd: YAG laser sold under the trade name “Scriba” from Electrorox, Indianopolis, Indiana. . However, other concentrated energy beam systems such as CO ₂ lasers and masers may be used. The marker 20 can be made with one or two passes of the laser beam, or with an additional laser beam pass if a somewhat wider field of the marker 20 is required. Multiple laser beam passes can also be used from multiple lasers or by laser beam splitting and focusing techniques. Suitable fixed distances to the outer surface 16 of the marker sleeve 10 of the laser system head range from about 2 centimeters (cm) to about 31 cm. The range is generally determined by the laser focus of the system. For example, the Nd: YAG laser system may exhibit a fixed distance of 18.3 cm (7.2 inches) to the marker sleeve 10 outer surface 16 of the laser system head.

Adjustment of the laser system causes the marker sleeve 10 to be sufficiently labeled on the outer surface 16 (ie to prevent under-labeling), but excessively heating or softening the underlying portion of the marker sleeve 10. So as not to over-label. It is important to maintain the structural integrity of the radial wall 11 of the marker sleeve 10 to prevent the possibility of tearing of the radial wall 11. The laser beam energy pulse should not adversely affect the ability of the marker sleeve 10 to remain stable over the cable 12. Examples of adjustments suitable for Nd: YAG laser systems include power adjustments in the range of about 55 watts to about 70 watts, label speeds in the range of about 5 centimeters / minute to about 7 centimeters / minute, and about one wave peak / second to about 10 waves Frequency in the peak / second range.

Laser labels enable important flexibility in the manufacture of identification labels (ie, the marker 20) both in terms of the information being labeled and in terms of product lead time and fixed costs. The flexibility of the laser marker makes it possible to individually tailor the markings 20 on the marker sleeve 10 to specific customer needs or specific market targets. The laser marker can be changed easily and quickly from one marker sleeve 10 to another marker sleeve 10. For example, digital information about the mark required by the customer can be entered into the computer program, which instructs the laser system to generate the laser mark. This allows for rapid onset and modification of the laser marker on demand.

After labeling, the marker sleeve 10 with the marker 20 is removed from the core 22 onto the cable 12. This can be done by any suitable known technique. In one embodiment shown in FIGS. 5 and 6, the cable 12 may be inserted into the hollow portion of the core 22, either before or after the laser marker. The cable 12 may be centered in cross section in the core 22 by guide fingers (not shown) contained within the core 22. After the cable 12 is inserted into the core 22, the marker sleeve 10 is carried from the core 22 onto the cable 12. This conveyance may be caused by sliding the marker sleeve 10 from the core 22 onto the cable 12, or by collapsing and removing the core 22 to cause the marker sleeve 10 to surround the cable 12, or the like. This can be done in a variety of ways.

As shown in FIG. 6, when the marker sleeve 10 is removed from the core 22, the marker sleeve 10 is cold contracted in a relaxed state from the expanded state. Whether the marker sleeve 10 arrives in a relaxed state depends on the diameter of the cable 12. As shown in FIG. 6, the cable 12 has a diameter that causes the marker sleeve 10 to return substantially in a relaxed state, as indicated by the inner diameter B and outer diameter C. As shown in FIG. Otherwise, the inner diameter B of the marker sleeve 10 in the relaxed state may be slightly smaller than the diameter of the cable 12. This choice prevents the marker sleeve from shrinking completely again in its relaxed state, thereby providing a generous and secure fit around the cable 12 of the marker sleeve 10.

The cross-sectional shrinkage of the marker sleeve 10 also shrinks the marker 20, as seen by comparing the marker portions 20a, 20b. When the portion of the marker sleeve 10 is retracted, the corresponding portion of the marker 20 (ie, the marker portion 20a) is also retracted while maintaining the inflated state supported on the core 22. The portion of 20 (ie, marker portion 20b) remains larger. When the marker sleeve 10 is retracted, the marker portion 20a is retracted with a cross-sectional dimension that is reduced from the inner diameter B 'and the outer diameter C'. However, the shrinkage of the marker portion 20a and the dimensional reduction of the resulting marker 20 do not render the marker 20 unreadable. For example, the portion of the marker 20 defined as a straight line when the marker sleeve 10 is in the inflated state is defined as a straight line when the marker sleeve 10 is substantially cold contracted back towards the relaxed state. Will keep things. Moreover, the reduction in the dimension of the mark 20 effectively increases the print density of the mark 20. As such, the marker portion 20a remains visually readable even when the marker sleeve 10 is in a substantially relaxed state, providing information about the cable 12.

The marker sleeve 10 is US Department of Defense Standard Practice MIL-STD-130K (2000), entitled "Identification Label of US Military Assets," and "Label of Electrical Insulating Material". It provides preferably an information sign (ie, a marker 20) that conforms to the SAE AS81531 aerospace standard of SAE International, Warrendale, Pennsylvania, each of which is incorporated herein by reference in its entirety. . The SAE AS81531 aerospace standard § 3.2.2 provides an example of a suitable printing surface height in the circumferential direction of the marker sleeve 10 in the relaxed state, which is from about 1.6 mm to about 0.9 mm for an outer diameter (C) of about 0.9 mm. A print surface height in the range of about 4.5 mm for an outer diameter C of 25 mm.

After being completely removed from the core 22, the marker sleeve 10 is cold contracted around the cable 12 as shown in FIG. 1. The marker 20 located above the outer surface 16 is sufficiently contrasted in color with the outer surface 16 to provide visual visual detection of the marker 20 and / or optical machine-readable detection of the marker 20. Make it possible. The marker 20 will also maintain visual readability even when the marker sleeve 10 is exposed to NBC material.

Property analysis and Characterization  Way

Various analytical techniques can be used to characterize the encapsulant material of the present invention. Some of the analytical techniques are used here. These analytical techniques are described next.

NBC  exam

A series of quantitative and qualitative tests related to nuclear, biological and chemical contaminant remaining capacity (NBCCS) requirements were performed to assess the chemical remaining capacity of the compositions of the present invention. The samples tested included corresponding marker sleeves extending around the plates and cables of the compositions of the present invention. The marker sleeve was prepared by extruding and crosslinking the composition of the present invention as described above.

The test was conducted on April 24, 1998, in accordance with the Test Operation Procedure (TOP) 8-2-111 entitled “Nuclear, Biological and Chemical (NBC) Contamination Remaining Ability, Small Item of Device”. It was performed by the UB Research Center (Calspan-UB Research Center, Inc., Buffalo, New York). The test was performed continuously and included pest desorption and contact measurement on the composition sample, and functional performance evaluation on the marker sleeve.

Physical property test

Physical properties relating to tensile modulus of elasticity (100%, 200% and 300%), tensile strength at break, elongation at break, Shore A hardness, and permanent cure percentage of the composition of the present invention, It was measured quantitatively to show durability. Tensile modulus (100%, 200% and 300%), tensile strength at break, and percent elongation at break were performed in accordance with ASTM D412-92. Shore A hardness test was performed according to ASTM D2240-03.

The permanent cure percentage test shows the amount of elastic recovery the material exhibits. For various composition mixtures of marker sleeves, dog bone shaped samples having an original length of 2.54 cm were formed using an ASTM D412-92 die C dumbbell cutter. The sample was then placed in a tensile cured fixture and stretched vertically to 200% (ie 100% strain) of its original length. This length (ie 5.08 cm) was recorded as the test length. The stretched sample was then maintained in the stretched dimension and placed at a temperature of 100 ° C. for 3 hours. The stretched sample was then cooled at a temperature of 21 ° C. for 1 hour. After cooling, the stretched sample was removed from the tensile cure fixture and cold contracted for 30 minutes at room temperature. The relaxed length was then measured. Permanent cure percentage was calculated by the following equation:

% Permanent Curing = 100x (relaxed length-original length) / (test length-original length)

Laser marker test

Visual readability of the label was qualitatively measured for marker sleeves formed from the compositions of the present invention according to the following method. The marker sleeve without marking was inflated onto the core having a diameter of 3.5 cm. Next, the inflated marker sleeve was laser labeled to mark the Nd: YAG laser system. The Nd: YAG laser system is a "Hi-Mark" No. "GSI Lumonics, Inc., Kanata, Ontario, Canada". It is marketed under the trade name 400. Laser adjustments for the Nd: YAG laser system included a power adjustment of 64.8 watts, a label speed of 5.1 cm / min, and a frequency of 6 wave peaks / second. The adjustment distance to the outer surface of the marker sleeve of the laser system head was 18.3 cm (7.2 inches). The marker was labeled such that in its relaxed state the marker exhibited a print-plane height of 2.0 mm in the circumferential direction of the marker sleeve.

After labeling, the marker sleeve was removed from the core and cold shrinked again substantially in the relaxed state. The marker on the marker sleeve was then visually observed by the naked eye of the human body in a substantially relaxed state. The marker is visually readable by the human eye (ie about 20/20 eyesight) from a mark on the marker sleeve (representing a print-plane height of 2.0 mm) from a distance of about 36 cm (about 14 inches) or more. It was considered acceptable.

The invention is described more particularly in the following examples, which are intended to be illustrative only, as many modifications and variations will be apparent to those skilled in the art within the scope of the invention. Unless indicated otherwise, all parts, percentages, and ratios reported in the Examples below are by weight, and all reagents used in the Examples are obtained from, or available from, the chemical sources described below, or Can be synthesized.

The following composition abbreviations are used in the following examples:

"Buna EPT 6850": Terpolymer of ethylene-propylene-diene monomer, commercially available from Bayer Chemical Corporation, Leverkusen, Germany.

"Buna EPT 8902": oil-extended 50% terpolymer of ethylene-propylene-diene monomers commercially available from Bayer Chemical Corporation (Leverkusen, Germany).

"Bannox ZMTI": R.T. An antioxidant derived from a 50% dispersion of zinc 2-mercaptotolimidazole in petroleum processing oils, commercially available from R.T. Vanderbilt Company, Inc., Norwalk, Connecticut.

"Stantone MB yellow": 50% dispersion of azo pigment CI pigment yellow 83 in ethylene-propylene rubber, marketed under the trade name "Stanton MB 11070 yellow" from PolyOne Corporation, Suwanee, Georgia .

"Struttol EF-44 A": Processing aid mixture of fatty acid metal soaps and amides, commercially available from Struktol Company of America, Stow, Ohio.

"LeoGran ZnO-85": solution of 85% active zinc oxide dispersion in inorganic oil, commercially available from Rhein Chemie Rheinau GmbH, Mannheim, Germany.

"Translink 37": Silane treated kaolin clay (aluminum silicate) with 1.4 micrometer particle size commercially available from Engelhard Corporation, Iselin, New Jersey.

"Hisil 532 EP": Hydrated amorphous silica filler commercially available from PPG Industries, Inc., Pittsburgh, Pennsylvania.

"Seytex BT-93 W": Flame retardant derived from 1,2-bis (tetrabromophthalimide) ethane commercially available from Albemarle Corporation, Houston, Texas.

"Sunpar 2280": paraffinic petroleum commercially available from Sunoco Inc., Philadelphia, Pennsylvania.

"Zinc Omadine": 65% 2-pyridinethiol-1-oxide, zinc complex (ie, zinc omadine) in paraffin oil, commercially available from Arch Chemicals, Inc., Cheshire, Connecticut. 65% antifungal solution.

"Nycol Burn EX ZTA": Sodium antimonite commercially available from Nyacol Nano Technologies, Inc., Ashland, Massachusetts.

"Tipure 902": E.I. Titanium dioxide, commercially available from Du Pont Corporation, Wilmington, Delaware.

"A-172 DLC": Silane coupling agent derived from vinyl-tris (2-methoxyethoxy) silane sold by Natrochem, Inc., Savannah, Georgia.

"Polyone Material": Laser additive derived from Stan-Tone MB-27838 Black, sold under the name "Polyone Material # AD 3000051160" from Polywon Corporation (Suwanee, Georgia).

"Barox 802-40KE": R.T. Peroxide crosslinkers derived from a solution of 40% active di (2-t-butylperoxyisopropyl) benzene supported on silane modified clays commercially available from Vanderbilt Company (Norwalk, Connecticut).

"SR-297 methacrylate": derived from 1,3-butylene glycol-dimethacrylate commercially available from Sartomer Company, Inc., Exton, Pennsylvania under the trade name "SR-297" Acrylic auxiliary agent.

Example  One

Example 1 relates to a composition of the present invention. Table 1 provides the component concentrations of the composition of Example 1. The composition of Example 1 combines the components given in Table 1 in the first mixing step (except Barox 802-40KE peroxide and SR-297 methacrylate), and then combines the components in a 10D with a capacity of 220 liters. Prepared by mixing for 8 minutes at a temperature of 141 ° C. at a rate of 50 revolutions / minute in a two-wing tangential Banbury mixer. The composition mixture was then passed through a 25.4-cm extruder equipped with a 100 mesh sieve to remove undispersed particles.

Barox 802-40KE peroxide and SR-297 methacrylate were then added in the second mixing step, and the entire composition mixture was added at about 45 revolutions per minute in a 10D two-wing tangential Banbury mixer with a capacity of 220 liters. Mix for 3 minutes at a temperature of 102 ° C.

The marker sleeve of Example 1 was extruded through the 5.1-cm single-screw extruder having a composition-to-length ratio of 15, an extruder zone and die temperature of 80 ° C., and a rotational speed of 30 revolutions / minute. Formed. After exiting the extruder, the extruded article was crosslinked by passing it through an autoclave with a water vapor pressure of 620 kilopascals for 45 minutes.

ingredient Weight percentage ^* Buna EPT 6850 21.7 Buna EPT 8902 18.6 Banox ZMTI 0.6 Stanton MB Yellow 1.9 Structol EF-44 A 0.6 Leogrand ZnO-85 1.2 Translink 37 6.2 Hisil 532 EP 12.4 Setex BT-93W 14.9 Wave 2280 12.4 Zinc Omardine 0.2 Nicole Burn EX ZTA 2.5 Tipure 902 3.1 A-172 DLC 0.3 Barox 802-40KE 2.2 SR-297 methacrylate 1.2 ( ^* ) Based on the total weight of the composition mixture of Example 1

Example  2

Example 2 relates to the composition of Example 1, further comprising a laser additive Stan-Tone MB-27838 black (ie, polysource material # AD 3000051160) (added in the first mixing step) in the composition. Table 2 provides the component concentrations of the composition of Example 2. The marker sleeve was formed from the composition of Example 2 following the method described for the marker sleeve of Example 1.

ingredient Weight percentage ^* Buna EPT 6850 22.4 Buna EPT 8902 19.2 Banox ZMTI 0.6 Stanton MB Yellow 1.9 Structol EF-44 A 0.6 Leogrand ZnO-85 1.3 Translink 37 6.4 Hisil 532 EP 12.8 Setex BT-93 W 15.4 Wave 2280 12.8 Zinc Omardine 0.2 Nicole Burn EX ZTA 2.6 A-172 DLC 0.3 Polyelement 0.1 Barox 802-40KE 2.2 SR 297 methacrylate 1.2 ( ^* ) Based on the total weight of the composition mixture of Example 2

Example  3

Example 3 relates to the composition of Example 2, further comprising Tipuro 902 titanium dioxide in the composition (added in the first mixing step). Table 3 provides the component concentrations of the composition of Example 3. The marker sleeve was formed from the composition of Example 3 following the method described for the marker sleeve of Example 1.

ingredient Weight percentage ^* Buna EPT 6850 21.7 Buna EPT 8902 18.6 Banox ZMTI 0.6 Stanton MB Yellow 1.9 Structol EF-44 A 0.6 Leogrand ZnO-85 1.2 Translink 37 6.2 Hisil 532 EP 12.4 Setex BT-93 W 14.9 Wave 2280 12.4 Zinc Omardine 0.2 Nicole Burn EX ZTA 2.5 Tipure 902 3.1 A-172 DLC 0.3 Polyelement 0.1 Barox 802-40KE 2.2 SR-297 methacrylate 1.2 ( ^* ) Based on the total weight of the composition mixture of Example 3

Example  About 1-3 NBC  exam

Marker sleeves made from the compositions of Examples 1-3 and the compositions of Examples 1-3 were NBCCS tested according to the "NBC Test" method described above. The marker sleeves made from the compositions of Examples 1-3 and the compositions of Examples 1-3 met NBCCS requirements. This is believed to be due to the combination of EPDM rubber, flame retardants and antibacterial agents. As such, the compositions of Examples 1-3 are NBC resistant and can be used to make articles that can be used in hazardous environments containing NBC materials.

Example  Physical property test for 1-3

The marker sleeves of Examples 1-3 were tested according to the "Physical Properties Test" described above. Table 4 provides the results of the physical property test for marker sleeves made from the compositions of Examples 1-3. Tensile modulus (100%, 200% and 300%) and tensile strength at rupture have metric units of meganewtons per square meter (MN / m ² ) (ie 1 × 10 ⁶ Newtons per square meter).

Physical properties Example 1 Example 3 Example 2 100% modulus of elasticity (MN / m ² ) 1.13 1.05 1.21 200% modulus of elasticity (MN / m ² ) 1.74 1.59 1.91 300% modulus (MN / m ² ) 2.31 2.11 2.48 Tensile Strength at Break (MN / m ² ) 6.14 5.13 6.20 Elongation at break% 717 715 732 Shore A Hardness 52.0 50.0 52.0 Permanent curing% 16.2 16.0 16.5

The data given in Table 4 shows the expansion capacity and durability of the articles made from the compositions of Examples 1-3 (ie, marker sleeves). The marker sleeves of Examples 1-3 have 100% tensile modulus of from 1.05 MN / m ² to 1.21 MN / m ² , 200% tensile modulus of from 1.59 MN / m ² to 1.91 MN / m ² , and from 2.11 MN / m ² to A 300% tensile modulus of 2.48 MN / m ² was shown. The marker sleeves of Examples 1-3 exhibited elongation at break of 715% to 732% with tensile strength at break of 5.13 MN / m ² to 6.20 MN / m ² . The marker sleeves of Examples 1-3 also exhibited a Shore A hardness of about 50.

The marker sleeves of Examples 1-3 also exhibited a permanent cure percentage of about 16%. As such, when subjected to the Permanent Curing Percentage Test as described above, the marker sleeves of Examples 1-3 may be recollapsed by about 84% to about 90% from their expanded state dimensions.

Example  Laser Marking Test for 1-3

The marker sleeves of Examples 1-3 were tested according to the "Laser Labeling Test" method described above. After substantially shrinking the marker sleeve of Example 1-3 in its relaxed state again, the mark on each marker sleeve was still visually readable to the human eye at a distance of at least 36 cm (about 14 inches). This shows the benefit of labeling the marker on the marker sleeve of the present invention in the expanded state. When labeling a label when the marker sleeve is in an expanded state, a higher degree of detail and resolution of the label is obtained, which reduces the precision of the label required to make the label. The mark obtained is still visually readable when the marker sleeve is substantially cold shrinked in a relaxed state.

While the invention has been described with reference to preferred embodiments, those skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the invention.

Claims (33)

Terpolymers of ethylene-propylene-diene monomers; Flame retardant; And A composition comprising an antimicrobial agent. The composition of claim 1 further comprising a flame retardant synergist. The composition of claim 1, wherein the flame retardant comprises 1,2-bis (tetrabromophthalimide) ethane. The composition of claim 1, wherein said antimicrobial agent comprises a pyrithione salt complex. The method of claim 1, Terpolymers of ethylene-propylene-diene monomers comprise from about 30.0% to about 80.0% by weight of the composition; The flame retardant comprises about 10.0% to about 30.0% by weight of the composition; Wherein the antimicrobial agent comprises from about 0.1% to about 0.4% by weight of the composition. The composition of claim 1 further comprising a filler material selected from silica, clay, and combinations thereof. 7. The composition of claim 6 further comprising a silane coupling agent. The composition of claim 1 further comprising a peroxide. The composition of claim 8, further comprising an acrylic adjuvant. 9. The composition of claim 8 further comprising zinc oxide. The method of claim 1, Flame retardant synergists; Antioxidants; And A composition further comprising a hydrocarbon oil. 12. The composition of claim 11, wherein the flame retardant comprises 1,2-bis (tetrabromophthalimide) ethane. The composition of claim 11 wherein the antimicrobial agent comprises a salt complex of pyrithione. The method of claim 11, wherein based on the total weight of the composition, Terpolymers of ethylene-propylene-diene monomers comprise from about 30.0% to about 80.0% by weight of the composition; The flame retardant comprises about 10.0% to about 30.0% by weight of the composition; The flame retardant synergist comprises about 1.0% to about 4.0% by weight of the composition; The antimicrobial agent comprises about 0.1% to about 0.4% by weight of the composition; The antioxidant comprises about 0.5% to about 2.0% by weight of the composition; Wherein the hydrocarbon oil comprises from about 10.0% to about 25.0% by weight of the composition. The composition of claim 11 further comprising a filler material selected from silica, clay, and combinations thereof. The composition of claim 15 further comprising a silane coupling agent. The composition of claim 11 further comprising a peroxide. 18. The composition of claim 17, further comprising an acrylic aid. 18. The composition of claim 17, further comprising zinc oxide. The composition of claim 11 further comprising a pigment and an energy beam absorber. 21. The composition of claim 20, wherein said energy beam absorber comprises a laser beam absorbent. Terpolymers of ethylene-propylene-diene monomers, mixtures of flame retardants, antibacterial agents, pigments and energy beam absorbers; And An article having a surface, comprising a concentrated energy beam-induced marker located on the surface. The article of claim 22, wherein the article comprises a tubular article and the surface comprises an outer surface. The article of claim 22 further comprising a flame retardant synergist. The article of claim 24, wherein the flame retardant comprises 1,2-bis (tetrabromophthalimide) ethane. The article of claim 24, wherein the antimicrobial agent comprises a salt complex of pyrithione. 23. The article of claim 22, wherein the concentrated energy beam comprises a laser, wherein the energy beam absorber comprises a laser beam absorbent. An expanded tubular article having an outer surface, The tubular article comprises a mixture comprising terpolymers of ethylene-propylene-diene monomers, flame retardants, antibacterial agents, pigments and energy beam absorbers; And Includes a concentrated energy beam-induced marker located on an outer surface and can be placed in a relaxed state, The marker is readable to the naked eye of an individual having a vision of 20/20 located at a distance of at least about 32 centimeters from the marker when the tubular article is in the expanded state and when the tubular article is in the relaxed state. Tubular goods. 29. The article of claim 28, further comprising a flame retardant synergist. The article of claim 28, wherein the energy beam absorber comprises a laser beam absorbent. Providing a tubular article comprising terpolymers of ethylene-propylene-diene monomers, flame retardants, antibacterial agents, pigments and energy beam absorbers; Expanding the tubular article from the relaxed state to the expanded state; Use the energy beam focused on the outer surface to form the marker; And shrinking the tubular article from its expanded state at low temperatures. 32. The method of claim 31, wherein providing the tubular article comprises extruding and crosslinking a mixture comprising terpolymers, flame retardants, antimicrobials, pigments, and energy beam absorbers of ethylene-propylene-diene monomers to form tubular articles. . 32. The method of claim 31 wherein the concentrated energy beam comprises a laser beam.

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