LOW MODULUS, HIGH ELONGATION STRUCTURAL ADHESIVES AND ASSOCIATED BONDED SUBSTRATES

Abstract

A substrate assembly, including: (a) a first substrate; (b) a second substrate; and (c) a thermosetting adhesive associated with at least a portion of the first and second substrates, wherein the thermosetting adhesive includes a curing agent, and an epoxy-modified dimerized fatty acid combined with an epoxy terminated polyurethane interpenetrating network.

Claims

1. A substrate assembly, comprising: a first substrate; a second substrate; and a thermosetting adhesive associated with at least a portion of the first and second substrates: wherein the thermosetting adhesive has been formulated based on epoxy-modified dimerized fatty acids combined with an epoxy terminated polyurethane interpenetrating network (IPN) and a diglycidylether of bisphenol-A; wherein the thermosetting adhesive exhibits extremely low modulus and high elongation; and wherein the thermosetting adhesive absorbs energy produced during distortion of similar and/or dissimilar metal which occurs during an e-coat oven curing process and/or any dynamic climate condition.

2. A substrate assembly, comprising: a first substrate; a second substrate; and a thermosetting adhesive associated with at least a portion of the first and second substrates, wherein the thermosetting adhesive includes a curing agent, and an epoxy-modified dimerized fatty acid combined with an epoxy terminated polyurethane interpenetrating network.

3. The substrate assembly according to claim 2, wherein the first and second substrates comprise similar metals.

4. The substrate assembly according to claim 2, wherein the first and second substrates comprise dissimilar metals.

5. The substrate assembly according to claim 2, wherein the first substrate comprises at least one of steel, steel electrogalvanized with zinc, steel hot dipped galvanized with zinc, aluminum, metal alloys, d-block metals, and combinations thereof.

6. The substrate assembly according to claim 2, wherein the second substrate comprises at least one of steel, steel electrogalvanized with zinc, steel hot dipped galvanized with zinc, aluminum, metal alloys, d-block metals, and combinations thereof.

7. The substrate assembly according to claim 2, wherein the first substrate comprises aluminum and the second substrate comprises steel.

8. The substrate assembly according to claim 2, wherein the curing agent comprises at least one of a boron trifluoride-amine complex, an organic-acid hydrazide, and dicyandiamide.

9. The substrate assembly according to claim 2, wherein the curing agent is represented by at least one of the following tautomeric chemical structures: ##STR00015##

10. The substrate assembly according to claim 2, wherein the epoxy-modified dimerized fatty acid is represented by the following chemical structure: ##STR00016## wherein R.sub.1 comprises an alkyl, cycloalkyl, polycycloalkyl, heterocycloalkyl, aryl, alkaryl, aralkyl, alkoxy, alkanoyl, aroyl, alkenyl, alkynyl and/or cyano group containing approximately 1 to approximately 40 carbon atoms.

11. The substrate assembly according to claim 2, wherein the epoxy-modified dimerized fatty acid is represented by the following chemical structure: ##STR00017## wherein R.sub.1 comprises an alkyl, cycloalkyl, polycycloalkyl, heterocycloalkyl, aryl, alkaryl, aralkyl, alkoxy, alkanoyl, aroyl, alkenyl, alkynyl and/or cyano group containing approximately 35 to approximately 40 carbon atoms.

12. The substrate assembly according to claim 2, wherein the epoxy-modified dimerized fatty acid is represented by the following chemical structure: ##STR00018## wherein R.sub.1 is tall oil based.

13. The substrate assembly according to claim 2, wherein the epoxy terminated polyurethane interpenetrating network is represented by the following chemical structure:
A.sub.1-R.sub.1-A.sub.2 wherein A.sub.1 is represented by the following chemical structure: ##STR00019## wherein R.sub.1 comprises an alkyl, cycloalkyl, polycycloalkyl, heterocycloalkyl, aryl, alkaryl, aralkyl, alkoxy, alkanoyl, aroyl, alkenyl, alkynyl and/or cyano group containing approximately 1 to approximately 75 carbon atoms, an oligomer, and/or a polymer; and wherein A.sub.2=A.sub.1 and/or comprises an alkyl, cycloalkyl, polycycloalkyl, heterocycloalkyl, aryl, alkaryl, aralkyl, alkoxy, alkanoyl, aroyl, alkenyl, alkynyl and/or cyano group containing approximately 1 to approximately 35 carbon atoms, an oligomer, and/or a polymer.

14. The substrate assembly according to claim 2, wherein the epoxy terminated polyurethane interpenetrating network is represented by the following chemical structure:
A.sub.1-R.sub.1-A.sub.2 wherein A.sub.1 is represented by the following chemical structure: ##STR00020## wherein R.sub.1 comprises an alkyl, alkenyl, and/or alkynyl group containing approximately 1 to approximately 36 carbon atoms, an oligomer, and/or a urethane polymer; and wherein A.sub.2=A.sub.1.

15. A substrate assembly, comprising: a first substrate; a second substrate; a thermosetting adhesive associated with at least a portion of the first and second substrates, wherein the thermosetting adhesive includes a curing agent, and an epoxy-modified dimerized fatty acid combined with an epoxy terminated polyurethane interpenetrating network; wherein the curing agent is represented by at least one of the following tautomeric chemical structures: ##STR00021## wherein the epoxy-modified dimerized fatty acid is represented by the following chemical structure: ##STR00022## wherein R.sub.1 comprises an alkyl, cycloalkyl, polycycloalkyl, heterocycloalkyl, aryl, alkaryl, aralkyl, alkoxy, alkanoyl, aroyl, alkenyl, alkynyl and/or cyano group containing approximately 35 to approximately 40 carbon atoms; and wherein the epoxy terminated polyurethane interpenetrating network is represented by the following chemical structure:
A.sub.1-R.sub.1-A.sub.2 wherein A.sub.1 is represented by the following chemical structure: ##STR00023## wherein R.sub.1 comprises an alkyl, alkenyl, and/or alkynyl group containing approximately 1 to approximately 36 carbon atoms, an oligomer, and/or a urethane polymer; and wherein A.sub.2=A.sub.1.

16. The substrate assembly according to claim 15, wherein the first substrate comprises aluminum and the second substrate comprises steel.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Certain embodiments of the present invention are illustrated by the accompanying figures. It will be understood that the figures are not necessarily to scale and that details not necessary for an understanding of the invention or that render other details difficult to perceive may be omitted. It will be further understood that the invention is not necessarily limited to the particular embodiments illustrated herein.

[0034] The invention will now be described with reference to the drawings wherein:

[0035] FIG. 1 is a perspective view of an automobile having two dissimilar substrates secured together with an adhesive of the present invention;

[0036] FIG. 2 is a perspective view of a substrate assembly fabricated in accordance with the present invention showing bond and load lines;

[0037] FIG. 3 of the drawings is a cross-sectional schematic representation of a substrate assembly fabricated in accordance with the present invention;

[0038] FIG. 4 of the drawings is a two-dimensional plot showing deflection as a function of load for Example 3 (similar substrate/low bake);

[0039] FIG. 5 of the drawings is a two-dimensional plot showing deflection as a function of load for Example 3 (similar substrate/high bake);

[0040] FIG. 6 of the drawings is a two-dimensional plot showing deflection as a function of load for Example 3 (dissimilar substrate/low bake);

[0041] FIG. 7 of the drawings is a two-dimensional plot showing deflection as a function of load for Example 3 (dissimilar substrate/high bake);

[0042] FIG. 8 of the drawings is a two-dimensional CLTE plot showing dimension change as a function of temperature for Example 6 (1.sup.st heating); and

[0043] FIG. 9 of the drawings is a two-dimensional CLTE plot showing dimension change as a function of temperature for Example 6 (2.sup.nd heating);

[0044] FIG. 10 of the drawings is a .sup.1H-NMR spectrogram of a first tautomer of a curing agent;

[0045] FIG. 11 of the drawings is a .sup.13C-NMR spectrogram of a first tautomer of a curing agent;

[0046] FIG. 12 of the drawings is a .sup.1H-NMR spectrogram of a second tautomer of a curing agent;

[0047] FIG. 13 of the drawings is a .sup.13C-NMR spectrogram of a second tautomer of a curing agent;

[0048] FIG. 14 of the drawings is a .sup.1H-NMR spectrogram of a curing agent;

[0049] FIG. 15 of the drawings is a .sup.13C-NMR spectrogram of a curing agent;

[0050] FIG. 16 of the drawings is a .sup.1H-NMR spectrogram of an epoxy-modified dimerized fatty acid curing agent;

[0051] FIG. 17 of the drawings is a .sup.13C-NMR spectrogram of an epoxy-modified dimerized fatty acid curing agent;

[0052] FIG. 18 of the drawings is a .sup.1H-NMR spectrogram of an A.sub.1 moiety; and

[0053] FIG. 19 of the drawings is a .sup.13C-NMR spectrogram of an A.sub.1 moiety.

DETAILED DESCRIPTION OF THE INVENTION

[0054] While this invention is susceptible of embodiment in many different forms, there is shown in the drawings and described herein in detail several specific embodiments with the understanding that the present disclosure is to be considered as an exemplification of the principles of the invention and is not intended to limit the invention to the embodiments illustrated.

[0055] It will be understood that like or analogous elements and/or components, referred to herein, may be identified throughout the drawings by like reference characters. In addition, it will be understood that the drawings are merely schematic representations of one or more embodiments of the invention, and some of the components may have been distorted from their actual scale for purposes of pictorial clarity.

[0056] As will be discussed and shown experimentally hereinbelow, the present invention is directed to unique epoxy hybrid structural heat curable adhesives that have been formulated based on epoxy-modified dimerized fatty acids combined with an epoxy terminated polyurethane interpenetrating network (IPN) and a standard liquid diglycidylether of bisphenol-A. The cured mechanical properties of the adhesives of the present invention are superior to conventional high rigid epoxy adhesives in OEM bonding applications of similar and dissimilar substrates.

[0057] Referring now to the drawings and to FIGS. 1-3 in particular, substrate assembly 100 is shown, which generally comprises first substrate 112 having first surface 112A and second surface 112B, second substrate 114 having first surface 114A and second surface 114B, and adhesive 116. It will be understood that substrate assembly 100 may comprise, for illustrative purposes only, an automobile component (See FIG. 1), and the like. It will be further understood that FIGS. 2-3 are merely schematic representations of substrate assembly 100. As such, some of the components have been distorted from their actual scale for pictorial clarity.

[0058] First substrate 112 may be fabricated from any one of a number of materials, such as, for example, steel, steel electrogalvanized with zinc, steel hot dipped galvanized with zinc, aluminum, metal alloys, d-block metals, and combinations thereof. First substrate 112 may also be fabricated from, for example, borosilicate glass, soda lime glass, float glass, natural and synthetic polymeric resins, plastics, and/or composites including Topas®, which is commercially available from Ticona of Summit, N.J. First substrate 112 is preferably fabricated from a sheet having a thickness ranging from approximately 0.25 mm to approximately 5.00 mm, and more preferably ranging from approximately 0.75 mm to approximately 2.50 mm. Of course, the thickness of the substrate will depend largely upon the particular application of the assembly. While particular substrate materials have been disclosed, for illustrative purposes only, it will be understood that numerous other substrate materials are likewise contemplated for use—so long as the materials exhibit appropriate physical properties, such as strength, to be able to operate effectively in conditions of intended use. Indeed, substrate assemblies in accordance with the present invention can be, during normal operation, exposed to extreme temperature variation, as well as substantial UV radiation, emanating primarily from the sun.

[0059] Second substrate 114 may be fabricated from similar and/or dissimilar materials as that of first substrate 112. As such, second substrate 114 may comprise polymers, metals, glass, and ceramics—to name a few. Second substrate 114 is preferably fabricated from a sheet having a thickness ranging from approximately 0.25 mm to approximately 5.00 mm, and more preferably ranging from approximately 0.75 mm to approximately 2.50 mm.

[0060] The present invention is directed to a substrate assembly that includes: (a) first substrate 112; and second substrate 114 bonded together by adhesive 116. Adhesive 116 is preferably a thermosetting adhesive that is associated (e.g., applied, impregnated, etch coated, dip coated, spin coated, brush coated and/or spray coated) with at least a portion of first and second substrates 112 and 114, respectively. Preferably, the thermosetting adhesive includes a curing agent (e.g., aliphatic curing agents, cycloaliphatic curing agents, polyamide curing agents, amidoamine curing agents, waterborne polyamides, latent curatives, tertiary amines, boron trifluoride-amine complexes, hydrazides, organic-acid hydrazides, dicyandiamide, etcetera), and an epoxy-modified dimerized fatty acid combined with an epoxy terminated polyurethane interpenetrating network.

[0061] In a preferred embodiment of the present invention, the curing agent is represented by at least one of the following tautomeric chemical structures:

##STR00008##

[0062] In this embodiment, the first tautomer of the curing agent generally comprises the .sup.1H-NMR spectrogram of FIG. 10 and/or the .sup.13C-NMR spectrogram of FIG. 11, and the second tautomer of the curing agent generally comprises the .sup.1H-NMR spectrogram of FIG. 12 and/or the .sup.13C-NMR spectrogram of FIG. 13.

[0063] In another preferred embodiment of the present invention, the curing agent is represented by the following chemical structure:

##STR00009##

[0064] In this embodiment, the curing agent generally comprises the .sup.1H-NMR spectrogram of FIG. 14 and/or the .sup.13C-NMR spectrogram of FIG. 15.

[0065] The above-identified curing agents and/or their precursors, are available from common commercial chemical vendors, such as Sigma-Aldrich Chemical Co., of St. Louis, Mo.

[0066] Suitable examples of epoxy-modified dimerized fatty acids include those represented by the following chemical structure:

##STR00010##

wherein R.sub.1 comprises an alkyl, cycloalkyl, polycycloalkyl, heterocycloalkyl, aryl, alkaryl, aralkyl, alkoxy, alkanoyl, aroyl, alkenyl, alkynyl and/or cyano group containing approximately 1 to approximately 40 carbon atoms. In one embodiment, R.sub.1 is tall oil based.

[0067] In another preferred embodiment of the present invention, the epoxy-modified dimerized fatty acid is represented by the following chemical structure:

##STR00011##

wherein R.sub.1 comprises an alkyl, cycloalkyl, polycycloalkyl, heterocycloalkyl, aryl, alkaryl, aralkyl, alkoxy, alkanoyl, aroyl, alkenyl, alkynyl and/or cyano group containing approximately 35 to approximately 40 carbon atoms.

[0068] In yet another preferred embodiment of the present invention, the epoxy-modified dimerized fatty acid is represented by the following chemical structure:

##STR00012##

wherein R.sub.1 is tall oil based (e.g., C.sub.36, C.sub.36H.sub.72, etcetera).

[0069] In this embodiment, the epoxy-modified dimerized fatty acid curing agent generally comprises the .sup.1H-NMR spectrogram of FIG. 16 and/or the .sup.13C—NMR spectrogram of FIG. 17.

[0070] The above-identified epoxy-modified dimerized fatty acid and/or its precursors, are available from common commercial chemical vendors, such as Sigma-Aldrich Chemical Co., of St. Louis, Mo.

[0071] In accordance with the present invention, suitable examples of epoxy terminated polyurethane interpenetrating networks include those represented by the following chemical structure:

A.sub.1-R.sub.1A.sub.2

wherein A.sub.1 is represented by the following chemical structure:

##STR00013##

wherein R.sub.1 comprises an alkyl, cycloalkyl, polycycloalkyl, heterocycloalkyl, aryl, alkaryl, aralkyl, alkoxy, alkanoyl, aroyl, alkenyl, alkynyl and/or cyano group containing approximately 1 to approximately 75 carbon atoms, an oligomer, and/or a polymer; and wherein A.sub.2=A.sub.1 and/or comprises an alkyl, cycloalkyl, polycycloalkyl, heterocycloalkyl, aryl, alkaryl, aralkyl, alkoxy, alkanoyl, aroyl, alkenyl, alkynyl and/or cyano group containing approximately 1 to approximately 35 carbon atoms, an oligomer, and/or a polymer.

[0072] In a preferred embodiment of the present invention, the epoxy terminated polyurethane interpenetrating network is represented by the following chemical structure:

A.sub.1-R.sub.1-A.sub.2

wherein A.sub.1 is represented by the following chemical structure:

##STR00014##

wherein R.sub.1 comprises an alkyl, alkenyl, and/or alkynyl group containing approximately 1 to approximately 36 carbon atoms, an oligomer, and/or a urethane polymer; and wherein A.sub.2=A.sub.1.

[0073] In this embodiment, A.sub.1 generally comprises the .sup.1H-NMR spectrogram of FIG. 18 and/or the .sup.13C-NMR spectrogram of FIG. 19.

[0074] The above-identified epoxy terminated polyurethane interpenetrating network and/or its precursors, are available from common commercial chemical vendors, such as Sigma-Aldrich Chemical Co., of St. Louis, Mo.

[0075] Additional interpenetrating polymer networks are also contemplated for use in accordance with the present invention, including, for example, those disclosed in U.S. Pat. No. 4,766,183 entitled “Thermosetting Composition for an Interpenetrating Polymer Network System,” U.S. Pat. No. 4,842,938 entitled “Metal Reinforcing Patch and Method for Reinforcing Metal,” U.S. Pat. No. 5,767,187 entitled “Interpenetrating Polymer Network Compositions,” U.S. Pat. No. 6,166,127 entitled “Interpenetrating Networks of Polymers,” U.S. Pat. No. 7,429,220 entitled “Golf Balls Containing Interpenetrating Polymer Networks,” and U.S. Pat. No. 7,790,288 entitled “Interpenetrating Polymer Network as Coating for Metal Substrate and Method Therefor”—which are hereby incorporated herein by reference in their entirety, including all references cited therein.

[0076] The invention is further described by the following examples.

Cured Mechanical Properties

Example/Test:

1. Lapshear Strength (MPa) (SAE J1523)

[0077] Material applied on oily substrate assembled as similar (1A) and dissimilar (1B) combination for 1″×0.5″, 0.01 bondline on 1″×3″ coupon. It is then baked at 171° C./10′ and 205° C./30′, then tested at room temperature (RT).

2. T-Peel Strength (N/mm) (ASTM D1876)

[0078] Material applied on oily substrate, assembled as similar (2A) and dissimilar (2B) combination for 1″×3″, 0.01″ bondline on 1″×′3″ coupon. It is then baked at 171° C./10′ and 205° C./30′, then tested at RT.

3. Wedge Impact Peel Strength (N/mm) (ISO 11343)

[0079] Material applied on oily substrate, assembled as similar (3A) and dissimilar (3B) combination for 20 mm×30 mm, 0.01″ bondline on 20 mm×90 mm coupon symmetric wedge. It is then baked at 171° C./10′ and 205° C./30′, then tested at RT.

4. Modulus of Elasticity (ASTM D638)

5. Elongation (ASTM D638)

6. Coefficient of Linear Thermal Expansion (CLTE) (ASTM E831-14)

Substrate:

[0080] 1. Electrogalvanized (0.7 mm) [0081] 2. Hot Dipped Galvanized (0.75 mm) [0082] 3. Aluminum (6022 Type) (0.9 mm) [0083] 4. Cold Rolled Steel (0.8 mm) [0084] 5. Aluminum (6016 Type) (1 mm) [0085] Oil: Ferrocote 6130 [0086] Bake Cycle: 171° C./10′ (metal type)//205° C./30′ (metal type)

Example 1A

Lapshear Strength (MPa)—Similar Substrate Combination

[0087] 1″×0.5″, 0.01″ bondline on 1″×3″ coupon

TABLE-US-00001 Low Bake High Bake Substrate (171° C./10′) (205° C./30′) Electrogalvanized (0.7 mm) + 16.88 15.01 Electrogalvanized (0.7 mm) 16.75 14.99 16.82 15.00 Hot Dipped Galvanized (0.75 mm) + 15.82 15.71 Hot Dipped Galvanized (0.75 mm) 15.77 15.53 15.79 15.62 Aluminum (6022 Type) (0.9 mm) + 17.64 17.30 Aluminum (6022 Type) (0.9 mm) 17.60 17.51 17.62 17.40 Cold Rolled Steel (0.8 mm) + 22.90 19.72 Cold Rolled Steel (0.8 mm) 21.61 20.78 22.25 20.25 Aluminum (6016 Type) (1 mm) + 16.33 18.11 Aluminum (6016 Type) (1 mm) 16.38 18.42 16.36 18.27

Example 2A

T-Peel Strength (N/mm)—Similar Substrate Combination

[0088] 1″×3″, 0.01″ bondline on 1″×4″ coupon

TABLE-US-00002 Low Bake High Bake Substrate (171° C./10′) (205° C./30′) Electrogalvanized (0.7 mm) + 12.26 10.21 Electrogalvanized (0.7 mm) 10.33 10.89 11.29 10.55 Hot Dipped Galvanized (0.75 mm) + 11.02 10.85 Hot Dipped Galvanized (0.75 mm) 11.56 10.23 11.29 10.54 Aluminum (6022 Type) (0.9 mm) + 11.41 11.13 Aluminum (6022 Type) (0.9 mm) 10.70 10.28 11.05 10.70 Cold Rolled Steel (0.8 mm) + 13.05 14.20 Cold Rolled Steel (0.8 mm) 12.58 12.78 12.81 13.49 Aluminum (6016 Type) (1 mm) + 11.28 10.03 Aluminum (6016 Type) (1 mm) 10.43 9.83 10.86 9.93

Example 3A

Wedge Impact Strength (N/mm)—Similar Substrate Combination

[0089] 20 mm×30 mm, 0.01″ bondline on 20 mm×90 mm coupon Test at RT

TABLE-US-00003 Low Bake High Bake Substrate (171° C./10′) (205° C./30′) Hot Dipped Galvanized (0.75 mm) + 33.58 41.03 Hot Dipped Galvanized (0.75 mm) 35.95 39.05 34.76 40.04 Aluminum (6022 Type) (0.9 mm) + 32.60 33.76 Aluminum (6022 Type) 0.9 mm) 31.92 34.03 32.26 33.89 Cold Rolled Steel (0.8 mm) + 35.58 32.18 Cold Rolled Steel (0.8 mm) 32.56 33.39 34.21 32.79 Electrogalvanized (0.7 mm) + 35.85 30.81 Electrogalvanized (0.7 mm) 31.89 31.11 33.87 30.96

[0090] See FIGS. 4 and 5 for corresponding low and high bake two-dimensional graphs.

Example 1B

Lapshear Strength (MPa)—Dissimilar Substrate Combination

[0091] 1″×0.5″, 0.01″ bondline on 1″×3″ coupon

TABLE-US-00004 Low Bake High Bake Substrate (171° C./10′) (205° C./30′) Electrogalvanized (0.7 mm) + 15.92 16.22 Hot Dipped Galvanized (0.75 mm) 16.02 16.37 15.97 16.30 Electrogalvanized (0.7 mm) + 16.72 17.11 Cold Rolled Steel (0.8 mm) 16.97 16.82 16.85 16.97 Cold Rolled Steel (0.8 mm) + 18.06 20.11 Aluminum (6022 Type) (0.9 mm) 17.66 19.82 17.86 19.97 Electrogalvanized (0.7 mm) + 16.37 17.77 Aluminum (6022 Type) (0.9 mm) 16.01 17.01 16.19 17.39 Hot Dipped Galvanized (0.75 mm) + 15.16 17.38 Aluminum (6022 Type) (1 mm) 16.22 16.92 15.69 17.15

Example 2B

T-Peel Strength (N/mm)—Dissimilar Substrate Combination

[0092] 1″×3″, 0.01″ bondline on 1″×4″ coupon

TABLE-US-00005 Low Bake High Bake Substrate (171° C./10′) (205° C./30′) Electrogalvanized (0.7 mm) + 12.56 9.35 Hot Dipped Galvanized (0.75 mm) 12.66 9.30 12.61 9.33 Electrogalvanized (0.7 mm) + 10.86 9.89 Cold Rolled Steel (0.8 mm) 10.85 10.25 10.85 10.07 Cold Rolled Steel (0.8 mm) + 11.00 9.40 Aluminum (6022 Type) (0.9 mm) 11.04 9.25 11.02 9.33 Electrogalvanized (0.7 mm) + 11.75 9.83 Aluminum (6022 Type) (0.9 mm) 11.90 9.91 11.83 9.87 Hot Dipped Galvanized (0.75 mm) + 11.83 9.38 Aluminum (6022 Type) (1 mm) 11.67 9.43 11.75 9.41

Example 3B

Wedge Impact Strength (N/mm)—Dissimilar Substrate Combination

[0093] 20 mm×30 mm, 0.01″ bondline on 20 mm×90 mm coupon

[0094] Test at RT

TABLE-US-00006 Low Bake High Bake Substrate (171° C./10′) (205° C./30′) Electrogalvanized (0.7 mm) + 31.45 28.91 Aluminum (6022 Type) (0.9 mm) 32.92 29.93 32.19 29.42 Hot Dipped Galvanized (0.75 mm) + 30.69 27.62 Aluminum (6022 Type) (1 mm) 31.31 27.82 31.00 27.72 Cold Rolled Steel (0.8 mm) + 29.55 28.28 Aluminum (6022 Type) (0.9 mm) 29.57 29.01 29.56 28.65

[0095] See FIGS. 6 and 7 for corresponding low and high bake two-dimensional graphs.

Examples 4 & 5

Modulus of Elasticity, GPa & Elongation (%)

[0096]

TABLE-US-00007 Modulus of Elasticity, GPa Elongation, (%) 0.458 53.23 0.416 51.45 0.437 52.34

Example 6

Coefficient of Linear Thermal Expansion (CLTE)

[0097]

TABLE-US-00008 Results To measure the coefficient of linear thermal expansion (CLTE) of sample by TMA per ASTM E831-14 as a guide. The sample was punched into a cylindrical shape and tested with a TMA Q400, TA instruments, equipped with an expansion probe (2.54 mm in diameter). A force of 20 mN was applied to the sample while heating the sample with a heating rate of 5.00° C./min in N2. TMA curves are shown in FIG. 1. Conclusion: The average CLTE (μm/(m .Math. ° C.) values calculated within a certain temperature range (brackets) are as follows. 1.sup.st heating 2.sup.nd heating CLTE-1 CLTE-2 CLTE-1 CLTE-2 102.6 223.8 99.40 219.2 (−60 to −10° C.) (20 to 160° C.) (−60 to −10° C.) (20 to 160° C.)

[0098] See FIGS. 8 and 9 for corresponding CLTE two-dimensional graphs.

[0099] While certain embodiments have been illustrated and described, it should be understood that changes and modifications can be made therein in accordance with ordinary skill in the art without departing from the technology in its broader aspects as defined in the following claims.

[0100] The embodiments, illustratively described herein may suitably be practiced in the absence of any element or elements, limitation or limitations, not specifically disclosed herein. Thus, for example, the terms “comprising,” “including,” “containing,” etcetera shall be read expansively and without limitation. Additionally, the terms and expressions employed herein have been used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the claimed technology. Additionally, the phrase “consisting essentially of” will be understood to include those elements specifically recited and those additional elements that do not materially affect the basic and novel characteristics of the claimed technology. The phrase “consisting of” excludes any element not specified.

[0101] The present disclosure is not to be limited in terms of the particular embodiments described in this application. Many modifications and variations can be made without departing from its spirit and scope, as will be apparent to those skilled in the art. Functionally equivalent methods and compositions within the scope of the disclosure, in addition to those enumerated herein, will be apparent to those skilled in the art from the foregoing descriptions. Such modifications and variations are intended to fall within the scope of the appended claims. The present disclosure is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled. It is to be understood that this disclosure is not limited to particular methods, reagents, compounds compositions or biological systems, which can of course vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

[0102] In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group.

[0103] As will be understood by one skilled in the art, for any and all purposes, particularly in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etcetera. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, etcetera. As will also be understood by one skilled in the art all language such as “up to,” “at least,” “greater than,” “less than,” and the like, include the number recited and refer to ranges which can be subsequently broken down into subranges as discussed above. Finally, as will be understood by one skilled in the art, a range includes each individual member.

[0104] All publications, patent applications, issued patents, and other documents referred to in this specification are herein incorporated by reference as if each individual publication, patent application, issued patent, or other document was specifically and individually indicated to be incorporated by reference in its entirety. Definitions that are contained in text incorporated by reference are excluded to the extent that they contradict definitions in this disclosure.

[0105] Other embodiments are set forth in the following claims.