Surface conforming activatable adhesive bodies and methods of making same

Abstract

A method for making an activatable material having a handling film layer thereon, comprising the steps of providing a continuous mass of a polymeric material having a longitudinal axis and being capable of adhering to a metal surface; applying a handling layer (e.g., film) over at least one side of the mass; forming stress relief indentations in the mass, with the handling layer at least partially extending into the indentations, wherein the stress relief indentations allow a resulting part to be applied in conforming geometry with a surface to which it is applied. The teachings also contemplate parts made by the above method and use thereof to bond to surfaces having a non-planar portion.

Claims

1. A method for making an activatable part, comprising the steps of: a) providing an activatable material mass of a polymeric material having a longitudinal axis and being tacky to the touch at room temperature, the activatable material mass having a base and an upper surface, wherein the base is adapted to adhere to a surface of a substrate; b) applying a handling layer over an entirety of the upper surface prior to activation of the activatable material mass; c) compressing the activatable material mass from the handling layer and upper surface toward the base to form a plurality of stress relief indentations in the activatable material mass prior to activation of the activatable material mass, with each stress relief indentation including the handling layer extending into the plurality of stress relief indentations so the entirety of the upper surface remains covered with the handling layer; wherein the plurality of stress relief indentations allow the activatable part to be applied to and conform to the surface of the substrate which is contoured and remain in place along the surface without pull back due to internal stress of the activatable part; and wherein the activatable part is configured to provide structural reinforcement, sealing, baffling, or a combination thereof to a cavity.

2. The method of claim 1, wherein the step of providing the activatable material mass includes extruding the activatable material mass through a die.

3. The method of claim 2, wherein the step of providing the activatable material mass includes extruding the activatable material mass through the die to define a rectangular profile.

4. The method of claim 3, wherein the step of providing the activatable material mass and the step of applying the handling layer are performed as continuous steps.

5. The method of claim 4, wherein the step of forming the plurality of stress relief indentations is performed by a device that includes a plurality of blades having tips for contacting the handling layer and applying pressure to the handling layer and the activatable material mass underlying it.

6. The method of claim 5, wherein the plurality of blades are separated by a resilient material that elastically deforms upon contacting the handling layer and applying pressure and which returns to its non-deformed state for causing any of the activatable material mass to be released from between the plurality of blades.

7. The method of claim 6, wherein each individual tip of the tips of the blades has a radius of curvature, a plurality of flat surfaces, or both.

8. The method of claim 7, wherein the blades are secured together parallel to each other, or wherein the blades are secured together so that they project radially outward from a hub.

9. The method claim 7, wherein the blades are secured together parallel to each other and the blades are reciprocally brought into contact with the handling layer; and wherein the activatable material mass with the handling layer thereon is successively advanced between the blades and an anvil by use of a stepper motor.

10. The method of claim 5, wherein the stress relief indentations are elongated and perpendicular to the longitudinal axis.

11. The method of claim 1, wherein a ratio of a height of the activatable part to a depth of the plurality of stress relief indentations ranges from about 1.5:1 to about 8:1.

12. The method of claim 11, wherein the activatable material mass is adapted to directly contact the substrate; and wherein the activatable material mass is adapted to directly bond to the substrate in the absence of a fastener.

13. The method of claim 12, wherein the method includes exposing the activable part to heat in a paint bake operation after application to the surface, during which the handling layer wets out and adheres to the surface and does not detract from the ability of the activatable part to seal the cavity.

14. The method of claim 1, wherein a depth of the plurality of stress relief indentations is about 2 to 3 mm and a height of the activatable part is about 3 to 4 mm.

15. The method of claim 14, wherein a lateral spacing of the plurality of stress relief indentations is about 0.5 to about 1.5 mm.

16. The method of claim 1, wherein the handling layer is a film which is tack free to the touch at room temperature.

17. The method of claim 16, wherein the film includes as a major component one or more of ethylene methyl acrylate copolymer, ethylene vinyl acetate copolymer, ethylene methacrylic acid copolymer, or a combination thereof.

18. The method of claim 17, wherein the film includes ethylene methyl acrylate copolymer as a major component, and further includes an oxidized synthetic paraffin.

19. The method of claim 16, wherein the step of applying the handling layer includes laminating the activatable material mass with the film so that the film is disposed on the entirety of the upper surface of the activatable material mass.

20. The method of claim 1, wherein the activatable material mass is a heat activatable, thermally expanding material.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a perspective view of an illustrative assembly operation for making parts in accordance with the present teachings.

(2) FIG. 2 is a side view illustrating the employment of parts herein on a surface of a component.

(3) FIG. 3 is an enlarged side view of parts in accordance with the teachings herein.

(4) FIG. 4a is a side view of a straight bladed tool useful in accordance with the present teachings.

(5) FIG. 4b is a partial side view of a rotary bladed tool useful in accordance with the present teachings.

(6) FIG. 5a is an enlarged view of an illustrative tip of a tool of FIG. 4a or FIG. 4b.

(7) FIG. 5b is an enlarged view of another illustrative tip of a tool of FIG. 4a or FIG. 4b.

(8) FIGS. 6a-6c are illustrations of applications of materials of the present teachings to a range of bend angles, and demonstrate how such materials remain bonded to an underlying substrate.

(9) FIG. 6d is an illustration of a part without indentations, which illustrates delamination of an overhang portion.

DETAILED DESCRIPTION

(10) The present teachings make use of a combination of materials that allow an activatable material to be readily manipulated into difficult locations, and around bends and/or curvatures of surfaces to which it is applied.

(11) In general, the teachings contemplate forming a mass of an activatable material (e.g., a heat activatable material). The mass of activatable material may have a longitudinal axis and a thickness.

(12) The mass of activatable material may be formed by extrusion, by molding (e.g., injection molding), or otherwise. A preferred approach is to extrude the activatable material so that it exhibits a substantially constant profile (e.g., a generally rectangular profile, a profile having generally rounded corners, or both). Profiles may have any suitable shape and/or dimension. By way of example, they may have a generally rectangular profile with a height to width ratio ranging from about 1:10 to about 1:2 (e.g., about 1:4, about 3:10 or about 2:5).

(13) Stress relief indentations are provided in at least one surface of the activatable material. The indentations may be generally perpendicular to the longitudinal axis. The indentations may penetrate a depth from an outer surface of the activatable material so that it is on the order of at least about 10%, 20%, 30% or higher of the overall thickness. The indentations may penetrate a depth from an outer surface of the activatable material so that it is on the order of less than about 70%, 60%, 50% or lower of the overall thickness.

(14) The indentations may be formed by a blade that is depressed into the activatable material. Two or more generally parallel blades may be employed. The blades may be retractable or otherwise translatable into and out of the activatable material.

(15) Optionally, a handling layer may be employed. The handling layer may cover one or more surfaces of the activatable material. The handling film may be a polymeric film that is capable of adheringly bonding to the activatable material. To the extent that the activatable material is tacky, the handling layer (e.g., film) may be such that it adhesively (and optionally, temporarily) bonds to the activatable material. The handling film may be generally tack free to the touch (e.g., at room temperature). Though described in a particular example as a film, the handling layer may be another form of material. For example, it may include a powder layer that is generally tack free to the touch at room temperature.

(16) The activatable material may be activated when subjected to heat during paint shop baking operations. In applications where the activatable material is a heat activated, thermally expanding material, an important consideration involved with the selection and formulation of the material comprising the activatable material is the temperature at which a material reaction or expansion, and possibly curing, will take place. For instance, in most applications, it is undesirable for the material to be reactive at room temperature or otherwise at the ambient temperature in a production line environment. More typically, the activatable material becomes reactive at higher processing temperatures, such as those encountered in an automobile assembly plant, when the material is processed along with the automobile components at elevated temperatures or at higher applied energy levels, e.g., during paint or e-coat curing or baking steps. While temperatures encountered in an automobile assembly operation may be in the range of about 148.89 C. to 204.44 C. (about 300 F. to 400 F.), body and paint shop applications are commonly about 93.33 C. (about 200 F.) or slightly higher. Following activation of the activatable material, the material will typically cure. Thus, it may be possible that the activatable material may be heated, it may then expand, and may thereafter cure to form a resulting foamed material.

(17) One or more sides of the activatable material may be tacky. Though it is also possible that one or more sides will be generally tack free to the touch at room temperature. One or more mechanical fasteners may be employed by attaching to or being formed integral with the activatable material.

(18) The teachings herein contemplate not only the method of making the parts herein, but also the method of using them. For example, the teachings contemplate attaching a part herein that includes the activatable material to a substrate (e.g., by adhesion from tackiness of the activatable material, by a fastener (e.g., a push pin fastener that is connected to the activatable material) or both). It will be seen, however, that by virtue of the geometries employed in accordance with the teachings, and by employment of a tacky activatable material, it is possible to avoid the need for any fastener. Thus, the methods herein may be free of a step of attaching with a fastener. The parts or resulting articles herein may be free of any fastener (e.g., they may be free of any mechanical fastener). The activatable material may be placed along a non-planar surface (e.g., a surface that is bent, folded or otherwise contoured), and due to the indentations may be able to substantially conform to the shape of the surface (e.g., over the contoured portion) while preserving the integrity of the activatable material mass (e.g., the mass may be deformed significantly around a contour, but will not rupture during installation into a vehicle cavity).

(19) The activatable material may be formed so that it will remain intact (without rupture) when bent around a body in excess of 90 to 180, in excess of 270 or even 300 (e.g., it may be essentially folded about an edge of sheet metal) relative to a distal end point of the activatable material. Stated alternatively, the substrate may have a plane that is defined originally by a first end portion and a second end portion. However the second end portion is bent at an apex relative to the plane. Thus, relative to the plane of the first end portion of the substrate material, the activatable material can be folded in excess of 90, or even in excess of 130, (e.g., from about 60 to about 140 relative to the plane of the first end portion of the substrate material) in order to closely conform to a surface with one or more bends or contours. The material will remain attached to substrate and will avoid spring back delamination, due to the absence of a buildup of internal stress within the material from the indentations. For sake of illustration, FIG. 2 illustrates folding of about 90 relative to the plane of the material (i.e., relative to the plane of the first portion of the substrate material. FIGS. 6a-6d also illustrate examples of approximate bend angles for activatable material relative to a first portion of the shown substrate. As seen the bend is in a direction away from the surface having the indentations. However, it may be possible to bend in the opposite direction while retaining the activatable material on the substrate. FIG. 6d illustrates an example of delamination of an overhang portion of the material.

(20) Suitable materials that may be employed for the activatable material mass include expandable materials and materials that do not expand. However, it is contemplated that the activatable material can be activated to form a foam. For instance, the material may be activated to form a structural foam (e.g., the material may include an epoxy ingredient). The material may be activated to form an acoustic foam. The material may be activated to flow for purposes of sealing a region within a cavity. The material may include a combination of a material that is activatable to expand and a material that is not activatable to expand.

(21) Materials that may be employed for the activatable material may include a polyolefinic material. It may include an ethylene-based material. For example, it may include one or any combination of an ethylene acrylic copolymer, ethylene acrylate copolymer, ethylene propylene ethylidene norbomene terpolymer, ethylene vinyl acetate copolymer, a brominated olefin polymer, ethylene-propylene containing materials (e.g., ethylene propylene dicyclopentadiene rubber, ethylene propylene copolymer, or both). The material may include one or more hydrocarbon resins. It may include an isobutylene/butene copolymer. It may include filler (e.g., calcium carbonate). It may include a blowing agent or other ingredients. An example of a suitable material that may be employed for the activatable material mass is L-2664 available from L&L Products, Inc. (Romeo, Mich.). The activatable material may be generally tacky to the touch at room temperature. It may be generally tacky to the touch at room temperature throughout substantially the entirety of its mass, along at least one outer surface, or both. An example of a suitable composition can be found in U.S. Application Ser. No. 61/837,832, filed Jun. 21, 2013, the contents of which are expressly incorporated by reference.

(22) An example of a suitable handling layer (e.g., film) may be made of a thermoplastic polymer (e.g., a vinyl, a polyolefin, a polyester or otherwise). One preferred material includes ethylene copolymer as a major component. For example, the layer may have as a major component one or more of ethylene methyl acrylate copolymer, ethylene vinyl acetate copolymer, ethylene methacrylic acid copolymer, or a combination thereof.

(23) The layer may contain one or more additional ingredients such as an oxidized synthetic paraffin, an epoxy (e.g., a diglycidyl ether bisphenol A epoxy), a hydrocarbon resin (e.g., an aromatic hydrocarbon resin), a filler, a curing agent, synthetic graphite, carbon black or any combination thereof. The layer may have a thickness below about 500 microns, below about 250 microns, or even below about 100 microns (e.g., it may be below about 50 microns). For example, the thickness may be about 0.02 to about 0.03 mm. An example of a suitable commercially available film is L-3801 or L-3803, available from L&L Products, Inc. (Romeo, Mich.). The layer may remain in place after installation into a vehicle cavity. It may be such that it will react and integrate itself with the underlying activatable material. Though not necessarily preferred, it is still possible that the handling layer (e.g., film) nonetheless may be at least partially removed over some or all of its length prior to activation of the activatable material. The handling layer may be provided in the form of a roll for lamination onto a mass of activatable material. The handling layer desirably may be sufficiently tough and strong that it will resist puncture during the formation of the indentations, and will withstand the induced bend (e.g., during a step of installation into an automotive vehicle) without rupture.

(24) The teachings thus contemplate that a mass of activatable material is provided with a handling layer (e.g., film). The mass (which may be extruded and have a generally constant profile along its longitudinal axis) may be subjected to pressure from one or more blades (e.g., blades that are sufficiently dull that they will not rupture the handling layer, but sufficiently strong that they will indent the mass of activatable material and effect penetration (and possibly stretching) of the handling layer into the activatable material. It is thus possible that the handling layer stretches as the blades press into the material, lining the walls of the indentations with stretched film. Thus, in general, resulting parts herein can have segments of plastically deformed film and film that is free of plastic deformation. The blades may be retractable, such that upon retraction, the handling film remains within the indentations. Tension relief can thus be provided as the overall material (activatable material with handling layer) is bent along a contoured surface defining a cavity into which the material is placed. The handling layer may also pull out of the indentations as needed, to help relieve surface tension as the part is stretched during installation.

(25) Lamination of the handling layer (e.g., film) to the activatable material may be done at room temperature. It is possible, however, that lamination can take place at an elevated temperature, e.g., above room temperature in the presence of heat.

(26) The ratio of the depth of indentations relative to the thickness of the mass of activatable material may be at least 1:10, 2:10, 3:10 or larger. The ratio of the depth of indentations relative to the thickness of the mass of material may be less than 9:10, 8:10, 7:10 or smaller.

(27) The indentation may extend along the entire width of the mass of activatable material. It may extend only partially along the width of the mass (e.g., over at least about 50% of the width). Indentations may be in spaced increments, e.g., in the range of about 2 to about 10 mm (e.g., about 5 mm).

(28) FIGS. 1 and 2 illustrate an example in accordance with the present teachings. An indented structure 10 is formed by one or more blades 12 that form indentations 14 to an activatable material 16. A handling layer (e.g., film) 18 is laminated (e.g., via a roll 20) ahead of the blades. The resulting activatable material may be attached to a substrate 22 (e.g., sheet metal of an automotive vehicle body). When the material bends around a corner it will not detach from the substrate as a result of internal stresses. As can be appreciated, this approach may employ a common carrier (e.g., a handling film layer) for a plurality of hinged segments. However, the carrier (e.g., the handling film) may be on only one side of activatable material, and the resulting structure may be free of activatable material on opposing sides of a carrier. Further as seen, a plurality of hinged segments may be possible, according to the teachings herein, in which the each of the segments contacts each adjoining segment.

(29) FIG. 3 illustrates an enlarged view of a part 10 in accordance with the present teachings. As seen, indentations 14 in a top surface separate the activatable material 16 into segments. The indentations have a depth (d), and the parts have an overall height (h). The height (h) may range from about 1.5 to about 8 mm or larger. For example, it may be about 3 to about 4 mm. The indentation penetrates the top surface to a depth that is about 1 to about 2 mm from the bottom surface of the part. Accordingly, the ratio of height to depth may range from about 1.5:1 to about 8:1.

(30) FIGS. 4a and 4b illustrate examples of blade arrangements for achieving the indentations. A plurality of blades 12 are aligned generally parallel to each other in FIG. 4a, with an optional elastic spacer material 26 disposed between them. A frame (not shown) carries the blades and spacer material in fixed relation to each other. In FIG. 4b, the blades 12 project radially outward from a hub 28 with an optional elastic spacer material disposed between them. The hub is adapted for rotational movement. In the course of manufacturing, for both of the above, the blades are brought into opposing relationship with an anvil, with the activatable material (with handling layer) disposed therebetween. Pressure causes indentations to form. The elastic spacer material serves to elastically deform in response to opposing forces while the activatable material is being compressed to form indentations. It effectively serves as a spring to then cause the activatable material (and handling layer) to be expelled from between blades. Material may be advanced for forming indentations by use of a stepper motor.

(31) FIGS. 5a and 5b illustrate examples of blade tips for the illustrative blades of FIGS. 4a and 4b. In FIG. 5a, it is seen that the blade tips may have chamfered corner surfaces 30 and a flat tip surface 32. In FIG. 5b, it is seen how a tip can have an arcuate surface 34.

(32) The blades of the example of FIG. 4b can be substituted for the blades of the example of FIG. 4a and vice versa.

(33) The manufacture of parts may be done on a generally continuous basis. For example, a profile of the activatable material may be extruded onto a layer of release paper. The handling layer may be laid over the activatable material. The resulting combination may then be subjected to application of pressure by the blades for forming indentations. The elastic material (e.g., a polymeric die foam) between blades may then expel any of the material that is lodged between the blades due to spring-like forces occasioned by the intrinsic material properties.

(34) Though a release layer may be employed for transport of the parts herein, the parts herein may be free of a carrier layer (e.g., free of a mesh tape or other like layer) that supports an underside of the activatable material when it is placed onto a substrate. As applied to a substrate, the part may consistent essentially of, or even consist of, the activatable material and the handling layer, wherein the handling layer is located distal of the substrate, while the activatable material is located proximate (or in direct contact with) the substrate.

(35) Parts may be applied to a substrate by removing the activatable material with handling layer thereon and applying a tacky side of activatable to a substrate. Suitable pressure may be applied to help assure at least a temporary bond between the activatable material and the substrate prior to subjecting to activation conditions. Thereafter, the substrate with the activatable material (and handling layer) thereon may be subjected to activation conditions (e.g., heat from an oven (e.g., a paint bake operation oven), at which time the activatable material will be activated to flow, foam, and/or cure, while also adheringly bonding to the substrate and possibly another adjoining or opposing substrate (e.g., substrates defining a cavity within a vehicle structure that is to be filled by the activatable material upon foaming).

(36) At a point of bending (e.g., at an apex in a bend of the substrate), there will be a first portion of the overall length of the activatable material on one side of the bend and a second portion of the overall length of the activatable material on the other side of the bend. The ratio of the length of the first portion to the second portion of the overall length may range from about 1:1 to about 10:1, and more preferably about 1:1 to about 5:1.

(37) The handling layer may be such that it is capable of at least partial plastic deformation in response to force applied during the formation of indentations. The handling layer may be such that when it is wrapped about a contoured surface the layer will withstand rupture. Thus, there may be some local elongation of the layer. In a bend, the handling layer may become partially removed from the underlying activatable material, while still remaining in bridging contact with the activatable material on sides opposite where the partial removal has occurred. In this manner, it is also possible that any separation of the activatable material that has occurred during bending can be kept in close proximity with each other, being kept in place by the film. Thus, during activation, any adjoining separated masses of the activatable material are positioned sufficiently close to each other so that they can bond to each other.

(38) As indicated elsewhere herein, during a step of activating the activatable material to form an activated material (e.g., a foam), the handling layer is such that it will wet out and cover at least a portion of the activated material. The handling layer effectively can become a part of an adhesive outer layer that can bond to an opposing substrate.

EXAMPLES

(39) By way of non-limiting example, to illustrate a technical benefit derived from the teachings herein, generally rectangular profiles of an activatable material having the composition of Table 1 are extruded and a handling layer having the composition of Table 2 is applied. The profiles range from about 3 to 5 mm in height and are 10 to 20 mm in width. Thus, the height to width ratio (as with the teachings elsewhere herein) may range from about 3:20 to about 1:2. The thickness of the handling layer is about 0.02 mm.

(40) The activatable material is applied to a steel substrate, which may have residual stamping oil thereon (e.g., Quaker Ferrocote 61MAOHC1). The activatable material is applied so that a length of about 50 mm of the sample is on one side of an apex defied by the bend, and an overhang length of about 15 mm is on the other side. Failure occurs when the overhang portion delaminates from the substrate (e.g., as seen in FIG. 6d).

(41) In general, materials having indentations are capable of withstanding bend angles on the order of about 60 larger than materials without the indentations. However, for some geometries, it may be possible to withstand bend angles of 100 or even 120 larger than materials without the indentations. For example, for a rectangular profile of 3 mm height and 10 mm width, indentation samples can remain bonded for about 24 hours to a steel substrate for a bend of approximately 180. In contrast, a like sized sample without indentations exhibits delamination at a substrate bend angle of about 80 over the same time period.

(42) TABLE-US-00001 TABLE 1 More Most Preferred preferred preferred parts by parts by parts by weight weight weight Ingredient (pbw) (pbw) (pbw) Masterbatch of: 23.5-27.5 25-26 25.45 Brominated Olefin Polymer (11.79 pbw)(e.g., Bromobutyl 2030 from Lanxess) Ethylene Propylene Ethylidene Norbornene Terpolymer (9.82 pbw)(e.g., Trilene 67 from Lion Coploymer) P-Aramide (0.2 pbw) (e.g., Kevlar 1F543 from DuPont) Ethylene-propylene dicyclopentadiene rubber (19.65 pbw) (e.g., Royalene 301T from Lion Copolymer) Ethylene Propylene Copolymer (7.86 pbw)(e.g., Vistalon 7001 from ExxonMobil) Ethylene Vinyl Acetate Copolymer (3.92 pbw) (e.g., Elvax 40W from DuPont) Ethylene Butyl Acrylate Copolymer Blend (19.65 pbw)(e.g., Elvaloy 34035EAC from DuPont or Lotryl 35BA40) Ethylene Acrylate Copolymer (7.86 pbw)(e.g., Elvaloy 4170 from DuPont) Carbon Black (1.18 pbw) (e.g., Raven 410 from Columbian Chemicals) hydrocarbon Resin (18.07 pbw)(e.g., Novares C-100 from Rutgers VFT AG) Severely Solvent Refined 9-13 10.5-11.5 11.00 Petroleum Hydrocarbon Oil (e.g., Sunpar 2280 from Sunoco) Polybutene (Isobutylene/butene 13-17 14-16 15.00 copolymer)(Indopol H-1500 from Ineos or TPC 1285 from Texas Petroleum) Modified Polyterpene Type 8.5-11 9-10.5 9.70 Hydrocarbon Resin (e.g., Wingtack 86 from Sartomer) Calcium Carbonate (e.g., GPR 325 26.5-30 28-28.5 28.16 or GFP 325 from Carmeuse or Hubercar Q325 from Huber) Azodicarbonamide (e.g., Azofoam 5-6.5 5.6-6.0 5.80 VI-30 or VC-30 from Otsuka or Celogen AZ120 from Lion Coplymer) Phenolic Resin(e.g., Resin P-101 0.5-1.5 0.9-1.1 1.00 from Akrochem) Dicyandiamide (e.g., Amicure 0.1-0.3 0.15-0.25 0.20 CG1200G from Air Products) Zinc Oxide, Nonferrous Metal 1-3 1.5-2.5 2.00 Oxide (e.g., Zoco 100 from Zochem or Kadox 930 from Horsehead) Dipentaerythritol Pentaacrylate 0.25-0.5 0.38-0.4 0.39 (e.g., SR399 from Sartomer) 1,1-bis(t-butylperoxy)-3,3,5- 0.8-1.6 1.1-1.3 1.20 trimethyl cyclohexane, carbonic acid calcium salt & calcium silicate (e.g., Luperox 231XL40 from Arkema) Dibenzoyl Peroxide & Dicyclohexyl 0.05-0.15 0.08-0.12 0.10 Phthalate (e.g., BP-50-FT from United Initiators)

(43) TABLE-US-00002 TABLE 2 More Most Preferred Preferred Preferred Parts by Parts by Parts by weight Weight Weight Ingredient (pbw) (pbw) (pbw) Ethylene Methyl Acrylate 48-55 50-53 51.3 Copolymer (e.g., EMAC SP2220 from Westlake) Oxidized Synthetic 17-23 19-21 20.7 Paraffin (e.g., Paraflint A28 from Moore & Munger, Sasolwax A28 from Sasol, or CWP-500 from Chusei Waxtech) DGEBPA-based polymer 2-4 2.8-3.2 3 (e.g., DER 661 from Dow) Dicumyl Peroxide (40%) & 0.5-1.5 0.8-1.2 1 Kaolin (60%) (e.g., DI- CUP 40KE from Arkema) Cyanoguanidine 0.18-0.22 0.15-0.25 0.2 (e.g., Amicure CG-325 or CG-325G from Air Products) Aromatic Hydrocarbon 6.5-8.5 7.0-8.2 7.7 Resin (e.g., Norsolene S- 105 from Sartomer, Nevex 1069 from Neville, Norsolene S-105E from Cray Valley or Bitoner BT- 100 from Aalchem) Ground High Calcium 14-18 15.5-16.5 16 Carbonate (e.g., Benwood Talc BT 2203 from IMI Fabi) Carbon Black (e.g., Raven 0.05-0.15 0.08-0.12 0.1 410 from Columbian Chemicals)

(44) General Comments

(45) As used herein, unless otherwise stated, the teachings envision that any member of a genus (list) may be excluded from the genus; and/or any member of a Markush grouping may be excluded from the grouping.

(46) Unless otherwise stated, any numerical values recited herein include all values from the lower value to the upper value in increments of one unit provided that there is a separation of at least 2 units between any lower value and any higher value. As an example, if it is stated that the amount of a component, a property, or a value of a process variable such as, for example, temperature, pressure, time and the like is, for example, from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, it is intended that intermediate range values such as (for example, 15 to 85, 22 to 68, 43 to 51, 30 to 32 etc.) are within the teachings of this specification. Likewise, individual intermediate values are also within the present teachings. For values which are less than one, one unit is considered to be 0.0001, 0.001, 0.01, or 0.1 as appropriate. These are only examples of what is specifically intended and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application in a similar manner. As can be seen, the teaching of amounts expressed as parts by weight herein also contemplates the same ranges expressed in terms of percent by weight. Thus, an expression in the of a range in terms of at least x parts by weight of the resulting composition also contemplates a teaching of ranges of same recited amount of x in percent by weight of the resulting composition.

(47) Unless otherwise stated, all ranges include both endpoints and all numbers between the endpoints. The use of about or approximately in connection with a range applies to both ends of the range. Thus, about 20 to 30 is intended to cover about 20 to about 30, inclusive of at least the specified endpoints.

(48) The disclosures of all articles and references, including patent applications and publications, are incorporated by reference for ail purposes. The term consisting essentially of to describe a combination shall include the elements, ingredients, components or steps identified, and such other elements ingredients, components or steps that do not materially affect the basic and novel characteristics of the combination. The use of the terms comprising or including to describe combinations of elements, ingredients, components or steps herein also contemplates embodiments that consist of, or consist essentially of the elements, ingredients, components or steps.

(49) Plural elements, ingredients, components or steps can be provided by a single integrated element, ingredient, component or step. Alternatively, a single integrated element, ingredient, component or step might be divided into separate plural elements, ingredients, components or steps. The disclosure of a or one to describe an element, ingredient, component or step is not intended to foreclose additional elements, ingredients, components or steps.

(50) It is understood that the above description is intended to be illustrative and not restrictive. Many embodiments as well as many applications besides the examples provided will be apparent to those of skill in the art upon reading the above description. The scope of the invention should, therefore, be determined not with reference to the above description, but should instead be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled. The disclosures of all articles and references, including patent applications and publications, are incorporated by reference for all purposes. The omission in the following claims of any aspect of subject matter that is disclosed herein is not a disclaimer of such subject matter, nor should it be regarded that the inventors did not consider such subject matter to be part of the disclosed inventive subject matter.