GB2038239A

GB2038239A - Metal-thermoplastic-metal laminates

Info

Publication number: GB2038239A
Application number: GB7944041A
Authority: GB
Original assignee: Monsanto Co
Current assignee: Monsanto Co
Priority date: 1978-12-22
Filing date: 1979-12-21
Publication date: 1980-07-23
Also published as: IT1126688B; FR2444563B1; GB2038239B; CA1141641A; AU529120B2; AU5414179A; SE7910589L; FR2444563A1; ES487111A1; SE446251B; DE2951784A1; BR7908461A; IT7928364A0

Abstract

This invention relates to a construction panel comprising a metal- thermoplastic resin-metal laminate and a process for preparing same, said laminates possessing in combination certain specified properties of coefficient of linear thermal expansion inelastic ratio and flexural stiffness, and having a specified maximum weight per m<2>, the ratio of the total thickness of the metal layers to the thickness of the thermoplastic resin lying within defined limits.

Description

SPECIFICATION Metal-thermoplastic-metal laminates cross-reference to related application This application is a continuation-in-part of copending application Serial No. 972,555 filed December 22, 1978.

BACKGROUND OF THE INVENTION Field of the invention This invention relates to laminates and a process for preparing same. More particularly, this invention relates to metal-thermoplastic-metal laminates having an improved combination of critical properties required for use in construction applications.

Description of the prior art Metal-thermoplastic-metal laminates and processes for their preparation are known. See, for example, Bugel et al., U.S. Patent 3,382,136; Zunich et al., U.S. Patent 3,353,742; Pohl et al., Modern Plastics, 41 (7 March) 119-124(1964); and M. Yoshida et al., Chemical Economy & Engineering Review, Vol. 2 No. 10 (October) 51-53,57 (1970).

The laminates described in the above-noted references, as well as other prior art laminates, however, are in general limited in their applications, particularly when contemplated for use as construction panels where the combination of low thermal expansivity (low coefficient of linear thermal expansion) and good recovery from flexural deflection (low inelastic ratio) are necessary properties of a laminate.

SUMMARY OF THE INVENTION A primary object of the present invention, therefore, is to provide a metal-thermoplastic-metal laminate having an improved combination of service properties considered important and critical for demanding construction applications such as outer and inner building panels, appliance panels, and transportation vehicle body panels, for example, automobiles, boats and airplanes.

A further object of the invention is to provide a construction panel laminate characterized by, among other properties, a combination of a low coefficient of linear thermal expansion, a low inelastic ratio (or high flexural elasticity), and very good strength in flexure.

A still further object of the invention is to provide such a laminate which, in addition to the critical properties deemed necessary for the construction applications, also has a wide range of additional desirable properties, for example, high heat distortion temperature, excellent deep-draw, simple-bend and formability at elevated temperatures, very good ductility, and very good energy absorption ability (including resistance to denting).

Another object of the invention is to provide a laminate having a specially selected thickness ratio of the sum of the metal layers thicknesseslthermoplastic core layer thickness for optimum combination of properties.

Still another object of the invention is to provide a laminate which is particularly adapted for use in automotive applications.

An additional object of the present invention is to provide a process for the preparation of the aforementioned metal-thermoplastic-metal laminates.

These and other objects will be apparent to those skilled in the art from the accompanying description and claims.

The above objects are successfully accomplished by the present invention which is directed to metal-thermoplastic-metal laminates having in combination: an inelastic ratio less than about 93 percent; a coefficient of linear thermal expansion less than about 63 x 10-s " C.-1; a flexural stiffness of at least about 52.53 x 103 N/m; and a maximum weight of no more than about 9.76 kg/m2; said laminate comprising: a thermoplastic core layer; and a metal layer laminated on each side of the thermoplastic core layer, each metal layer having a minimum thickness of about 0.00127 cm; provided that aluminum is not the metal layer on both sides of the laminate when the thermoplastic core layer is high density polyethylene and further provided that when polypropylene is the thermoplastic core and aluminum is the metal layer laminated on each side of the core, the laminate has a maximum weight of about 5.37 kg/m2; wherein the thickness ratio of the sum of the metal layer thicknesses to the thermoplastic core layer thickness is described by the region of numerical overlap of the parameter TR(YSm/TSC) as determined from the areas defined by the relationships of TR(YSm/TSC) to IR, and CLTE, the lower boundary of said areas being defined by the equation of a straight line y = mx + b in which y is they-axis parameters of IRe and CLTE6, xis the x-axis parameter of TR(YSm/TSC), m is the slope of the straight line, and b is the intercept on they-axis with the proviso that:: when y is IR6, m is 108 and b is zero (0) for values of x from zero (0) to 0.65, and m is zero (0) and b is 70 for values ofx greater than 0.65; and when y is CLTE,, m is -3.6:6 10-4 and b is 45 x 10-6forvalues of from zero (0) to 0.1, and mis zero (0) and b is 9 x 106forvalues of greaterthan 0.1; and the upper boundary of said areas being defined by the equation of a straight line as defined hereinabove, with the proviso that: when y is IR@m m is 280 and b is 30 for values of x from zero (0) to 0.25, and m is zero (0) and b is 100 for values of x greater than 0.25; and when y is CLTE6, m is -2.88 x 10-3 and b is 216 x 10-6forvalues of from zero (0) to 0.05, mis -1.29 x 10-4 and b is 78.5 x 10-8 for values of xfrom 0.05 to 0.26, and m is zero (0) and b is 45 x 10-6 for values ofx greater than 0.26; wherein: IR, is the inelastic ratio of the laminate as measure in flexure at 5% strain in the outer metal layers at the point of maximum deflection; CLTE, is the coefficient of linear thermal expansion of the laminate; TR is the thickness ratio of the sum of the metal layer-thicknesses to the thermoplastic core layer thickness; YSm is the thickness-weight-average tensile yield strength of the two metal layers at an offset of 5% elongation; and TSC is the tensile strength of the thermoplastic core layer.

Stated alternatively, the thickness ratio of the sum of the metal layer-thicknesses to the thermoplastic core layer thickness is described by the region of numerical overlap of the parameterTR(YSm/TSc) as determined from plots of IR, versus TR(YSmiTSC) and CLTE, versus TR(YSmiTSC) as shown, respectively, in Figures 1 and 2 of the specification, in which IR6, CLTE6, TR, York, and TSC are as defined hereinabove.

The provision of the process object is accomplished by a process which comprises: (a) disposing a metal layer on each side of a thermoplastic core layer, with the thickness ratio of the sum of the metal layer-thicknesses to the thermoplastic core layer thickness being determined as described hereinabove; (b) laminating the thermoplastic core layer and the metal layers by subjecting the combination to elevated temperatures and a pressure sufficient to maintain face-adhering contact; and (c) cooling to ambient temperatures.

BRIEF DESCRIPTION OF THE DRAWINGS The present invention will be more readily understood by reference to the accompanying drawings in which: Figure lisa plot correlating inelastic ratio, IR, with TR(YSm/TSC) for laminates both within and without the scope of the present invention; Figure 2 is a plot correlating coefficient of linear thermal expansion CLTE, with TR(YSm/TSC) for laminates both within and without the scope of the present invention; and Figure 3 is a plot correlating a normalized heat distortion temperature (HDT) variable (HDT, - HDTC)/Tmc HDTC), with TR(YSm/TSC) for laminates both within and without the scope of the present invention.

DETAILED DESCRIPTION OF THE INVENTION 1. Critical service properties The metal-thermoplastic-metal laminates of the present invention are constructed of a thermoplastic core layer and two metal layers, one laminated on each side of the thermoplastic core layer. The laminates are characterized by a combination of critical service properties ~~ low coefficient of linear thermal expansion, low inelastic ratio (good elasticity in flexure), and very good flexural stiffness, as well as certain other desirable properties, which make them excellent for use as construction panels.

Low coefficient of linear thermal expansion (CLTE,) [less than about 63 x 10-6cm/cm/ C. (oC.-1) (35 x 10-6 OF.-1)] is a critical property of the metal-thermoplastic-metal laminates of the present invention because in the construction applications contemplated, changes in part sizes due to temperature variations must be minimal in order to lessen the possibility of unsightly bulges and gaps between metal and concrete components and parts made with the laminates of this invention. The coefficient of linear thermal expansion is measured according to ASTM D 696-70 test method for plastics. It can also be determined by measuring the distance between two finely scribed parallel lines on the surface of the specimen with a calibrated traveling microscope or cathetometer. The specimen is contained in a rectangular hole in a heavy copper block which can be thermostatically controlled at various, widely separated temperatures. The rectangular hole in the copper block is only slightly larger than the cross-section of the specimen, and the scribed lines on the surface of the specimens are visible through a narrow slit machined into the copper block.

While certain plastic materials are lightweight and have high energy absorption capability (high impact strength), making them desirable for use as construction panels, they suffer from the disadvantage that their coefficients of linear thermal expansion are 4 to 5 and even 10 times that of most metallic and vitreous construction materials, for example, aluminum, steel, and concrete. Their use for construction panels on metal or concrete structural frames often are precluded by the high differential thermal expansivity which leads to problems of fastening, and, in addition, by the unsightly gaps which would result between panels at low temperatures and/or the buckling of panels at high temperatures.

The normal procedure for lowering the coefficient of linear thermal expansion of plastics is to incorporate glass fibers. Usually, 30 to 40 weight percent of glass is sufficient to reduce the coefficient of linear thermal expansion of a plastic to about that of aluminum (about 23.4 x 10-6 oC.-1). This, however, usually results in a strong but brittle material having very low elongation to break. That is, the composite cracks at very low impact regardless of whether the plastic per se is a strong but brittle resin, such as a thermostat polyester, or a tough polymer with high extensibility with high elongation to break, such as nylon 6, 6.It will be noted, however, that the decreased multiaxial impact resistance of glass-filled plastics does not preclude the use of glass fibres in the thermoplastic core layer materials of the present invention in that lamination of suitable metal layers thereon as described hereinbelow tends to offset (at least in part) the undesirable properties of the glass-filled thermoplastics.

Metals, of course, do not suffer the disadvantage of high coefficients of linear thermal expansion as do plastics. However, they generally are not lightweight, particularly at thicknesses sufficient for use as construction panels. Also, their elastic recovery from denting generally is very poor.

Thus, the metal-thermoplastic-metal laminates of the present invention provide the best of both worlds.

That is to say, they not only have a maximum weight of no more than 9.76 kg/m2(2 lb./ft.2) but in addition are characterized by a combination of low inelastic ratios (good flexural elasticities), very good flexural stiffness, and low coefficients of linear thermal expansion.The coefficient of linear thermal expansion must be less than 63 x 10-6 oC.-1. However, in certain applications requiring low thermal expansivity, such as in the case of an automobile panel, the CLTE, preferably is less than 54 x 10-6 oC.-1, and more preferably, less than 45 x 10-6 oC.-1. The low CLTE, values obtainable by the laminates of this invention (less than about 63 x 10-6 JC.-l), although somewhat yreater than those of steel (about 15.3 x 10-6 OC.-l) ,,d aluminum (about 23.4 x 10-6 C.-1), are sufficiently lowfordemanding construction applications.

An example of the low coefficient of linear thermal expansion exhibited by laminates of the present invention is as follows. A laminate (Example 2) comprised of two 0.0127 cm (0.005 inch, 5 mils) thick 1100-0 aluminum layers laminated, one on each side of a 0.157 cm (0.062 inch, 62 mils) thick polypropylene layer had a coefficient of linear thermal expansion of 23.6 x 10-6 C.1 compared to 23.6 x 10-6 C.1 compared to 23.6 x 10-6 oC.-1 for the aluminum alone and the relatively high value of 144.9 x 10-6 oC.-1 for the polypropylene alone.

Low inelastic ratio (irk) (good flexural elasticity) (less than about 93%) is a critical property of the metal-thermoplastic-metal laminates. The inelastic ratio characterizes the elastic recovery of such laminate panels after being subjected to deflection sufficient to produce a substantial strain (for example, 5%) in the outer metal layers at the point of maximum deflection. It is measured according to a specific modification of ASTM D 790-71.The method may be described as follows: A sheet specimen with rectangular cross-section of width b = 1.27 cm (0.5 inch), a thickness or depth d in cm (inches), and a length f = (L + 6), where L is the span of the flexural test in cm (inches) and E > 1.27 cm (0.5 inch), is set horizontally into a three-point flexural test fixture [i.e., with the 1.27 cm (0.5 inch) width horizontal and the depth d verticals and deflected at a crosshead deflection rate D of 0.0212 cm/s (0.5 inch/minute) to a deflection Do in cm (inches) such that the strain r in the central portion of the outer skin of the specimen is, except where noted otherwise, 5%, as computed in percent by the formula r = 600dDo/L2.

The span L used is approximately 16 times the depth d, except for thicknesses or depths d 0.172 cm (0.065 inches), whereupon the span used is 2.54 cm (1.00 inch). After bending the specimen to the specified deflection D,, the flexural loading is immediately removed at a crosshead deflection rate of 0.846 cm/s (20 inches/minute). Then the specimen is immediately removed from the flexural test fixture, set on its edge on a flat surface and allowed to freely relax. Periodically, the specimen is placed in a fixture with the same span and configuration used in bending it, and its residual deflection Dr is measured with a dial guage. When the residual deflection Dr has reached its limiting, equilibrium value, Dr = DR, the inelastic ratio is computed according to the formula IR = 100(DR/Do), in percent.The limiting, equilibrium value DR is attained usually within a period of one to two days, but always within one week.

As noted hereinabove, the inelastic ratio (IR,) is a critical and important characterization of the elastic recovery of laminate panels after they have been deflected sufficiently to produce substantial strain in their outer surfaces. If IR, is too high (low elasticity), both the degree of recovery of the laminates to their original shape after being strained substantially and the ability of the laminates to recover totally their original shape after being deflected in use to some lesser degree of strain will be inadequate under demanding use conditions. And, since one of the principal objects of the present invention is the provision of a metal-thermoplastic-metal laminate having an improved combination of service properties considered important and critical for demanding construction applications, an important limitation of the present invention is the upper limit on IR,.

In general, materials having an inelastic ratio greater than 93% are too inelastic and/or too weak to be employed as construction panels under conditions demanding or requiring any elasticity (or more specifically, elastic recovery) at all. The upper limit for the inelastic ratio of the laminates within the scope of the present invention is therefore 93%.Moreover, laminates having inelastic ratios in the following ranges, determined at 5% strain in the outer metal layers at the point of maximum deflection as described hereinabove, are rated as follows: Inelastic Ratios, IR, Rating > 93% very poor 84-93% marginal 75-84% fair 30-75% good < 30% excellent Since both the degree of recovery of the laminate to its original shape after being strained substantially and the ability of the laminate to totally recover without experiencing any permanent dents and creases after being strained to a small degree increase as the inelastic ratio decreases, the lower the inelastic ratio becomes the more desirable the laminate becomes for demanding construction applications. Thus laminates having inelastic ratios within the good and excellent ranges, that is, less than 75%, are preferred.

It will be recognized, of course, that while IR is employed herein is determined (except where noted otherwise) at a strain r of 5%, other strain values, either lower or higher, can be employed. However, IR values determined at strain values other than 5% generally will differ from those determined at 5%. For example, an IR value determined at a strain less than 5% (such as 1.5%) will in general be lower than that determined at 5%. Conversely, an IR value determined art a strain greater than 5% (such as 8%) generally will be higher than that determined at 5%.

It will be noted that the inelastic ratio for the laminates within the scope of the present invention, surprisingly, is always lower than that for the metal layer materials alone which have an inelastic ratio (IRm) upper limit of about 95% (for very soft 1145-0 aluminum). As an example, a laminate (Example 2) comprised oftwo 0.0127cm (0.005 inch, 5 mils) thick 1100-0 aluminum layers and a 0.0157 cm (0.062 inch, 62 mils) layer of polypropylene interposed therebetween and laminated thereto had an inelastic ratio of only 72% compared to the very high inelastic ratio of 94% obtained for sheets of 1100-0 aluminum alone.

As another example, a laminate (Example 26) comprised of two 0.0127cm (0.005 inch, 5 mils) thick 1100-0 aluminum layers and a 0.180 cm (0.071 inch, 71 mils) thick layer of nylon 6,6 interposed therebetween and having good adhesion thereto had an inelastic ratio of only 27% compared to the very high inelastic ratio of 94% characteristic of sheets of 1100-0 aluminum alone.

Good elasticity (low IR) and consequently good dent recovery, is therefore a prime characteristic of the laminates of the present invention, particularly when compared to conventional construction sheeting or panels made of metal alone.

Excellent flexural stiffness (as well as high flexural modulus, a measure of unit flexural stiffness) is a highly desirable property which the laminates must possess. This requirement is necessitated by the fact that the laminates must be sufficiently stiff so as to minimize the need for structural framing and/or to minimize flexural deflection of the laminate panels from wind, marine hydraulic, and other loads. The ability of the laminates to resist wind and hydraulic pressures is particularly significant when they are used,forexample, as automotive vehicle body panels, boat body panels, and as outer panels in building construction.

Flexural stiffness m is measured according to a specific version of ASTM D 790-71. The specific version can be described as follows: A sheet specimen with a rectangular cross-section of width b = 1.27 cm (0.5 inch), a thickness or depth d in cm (inches), and a length I = (L + e), where L is the span of the flexural test in cm (inches) and E > 1.27 cm (0.5 inch), is set horizontally into a three point flexural test fixture (i.e., with the 1.27 cm (0.5 inch) width horizontal and the depth d vertical) and deflected at a cross-head rate D of 0.00212 cm/s (0.05 inch/minute).

The applied load P in N (Ib.) is recorded, as the deflection D in cm (inches) increases at the specified constant rate. For thicknesses or depths d < 0.165 cm (0.065 inch), the span L is 2.54 cm (1.00 inch). Otherwise, the span is approximately 16 times the thickness or depth of the sheet specimen. The effective flexural modulus E5 in N/m2 (psi) is computed from the formula Ee = L3m,14bd3, where me in N/m (Ib.in.) is the experimental slope of the initial, linear portion of the load versus deflection curve. The flexural strength Sin N/m2 (psi) is computed from the formula S = 3PL/2bd2 unless otherwise specified, this strength is computed as the stress at which the strain in outer skin of the central portion of the specimen is r = 600dD/L2 = 5%.The flexural stiffness m is computed as m = 4bd3E e/L3 for the specific case of b = 2.54 cm (1.00 inch) and L = 2.54 cm (1.00 inch).

A flexural stiffness of about 52.53 :6 x 103 N/m (300 lb./in.) is the lowest value that can be utilized for sheeting or panels in most construction and building applications, even where framing is maximized and requirements on flexural deflection of the panels is minimal. This flexural stiffness is characteristic of 0.0508 cm (0.020 inch, 20 mils) thick sheets of relatively weak and inelastic 5052-0 aluminum weighing 1.37 kg/m2 (0.280 Ib./ft.2). This approximate lowest useful flexural stiffness of about 52.33 x 103 N/m is readily achieved with the laminates of the present invention.For example, as shown in the following table, a laminate (Example 44) comprised of two 0.0127 cm (0.005 inch, 5 mils) thick layers of 5052-0 aluminum laminated on each side of a 0.0711 cm (0.028 inch, 28 mils) thick layer of nylon 6,6 had a flexural stiffness of 161.44 x 103 N/m (922 Ib./in.) [an effective flexural modulus of 28.95 x 109 N/M2 (4.2 x 106 psi)l and a weight of 1.49 kg/m2 (0.306 Ib./ft.2) compared to a stiffness of 38.00 x 103 N/m (217 Ib./in.) for a 0.133 cm (0.0523 inch, 52.3 mils) thick sheet of nylon 6, 6 alone weighing 1.51 kg/m2 (0.310 lb./ft.2).

Thus, the laminate gives much higher stiffness than aluminum sheet of only slightly less weight per unit area and even higher stiffness relative to that of a much thicker sheet of nylon 6,6 alone having equivalent weight per unit area.

In a similar manner, also shown in the following table, a laminate (Example 2) comprised of two 0.0127 cm (0.005 inch, 5 mils) thick layers of 1100-0 aluminum (which is even softer and more inelastic than 5052-0 aluminum) laminated on each side of a 0.157 cm (0.062 inch, 62 mils) thick layer of polypropylene had a flexural stiffness of 329.19 x 103 N/m (1880 Ib./iin.) .[an effective flexural modulus of 8.26 x 109 N/m2 (1.26 x 106 psi)j and a weight of 2.10 kg/m2 (0.431 lb./ft.2) compared to a stiffness of 24.86 x 103 N/m (142 Ib./in.) for a 0.244 cm (0.096 inch, 96 mils) thick sheet of polypropylene alone weighing 2.20 kg/m2 (0.450 Ib./ft.2).

As can readily be seen, the laminate gives much higher stiffness than aluminum sheet of substantially equivalent weight per unit area and even higher stiffness relative to that of a sheet of polypropylene alone more than 1.3 times thicker and having substantially equivalent weight per unit area.

Flexural Effective Stiff- Flexural nessb Weightc Modulus Density m, W, EB D, Sheetinga 103 N/m kg/m2 109 N/m2 kg/m2cm 0.182 [0.0127, 1100-0 Al/Poly Propylene/1100 OAI] 329.19 2.10 8.69 -- 0.244 [0/Polypropylene/0] 24.86 2.20 0.28d 8.99e 0.577 [0/Poly propylene/0] 329.19 5.17 0.28 8.99e 0.00965 [0.0127, 5052-0 Al/Nylon 6,6/5052-0 Al] 161.44 1.49 28.95 ~~ 0.133 [0/nylon 6,6/0] 38.00 1.51 2.62d 11.37 0.152 [0.0152, 6061-T6 Al/ nylon 6,6/6061 T6 Al] 606.72 2.21 27.64 -0.194 [0/nylon 6,6/0] 117.84 2.20 2.62d 11.37 0.147 [0.0127, 1100-0 Al/Polycarbonate/1100 OAI] 301.87 2.22 15.24 ~~ 0.180 [0/Poly- carbonate/0] 92.80 2.20 2.55 12.17e 0.268 [0/Polycarbonate/0] 301.87 3.25 2.55 12.17e 0.172 [0.0127, 1100-0 Al/PVC/ 1100-OAI] 453.68 2.79 14.20 ~~ 0.155 [0/PVC/0] 79.67 2.20 3.38d 14.25e Flexural Effective Stiff- Flexural nessb Weight CModulus Density m, VV, Es D, Sheetinga 103 N/m kg/m2 109 N/m kg/m2cm 0.279 [0/PVC/0] 453.68 3.98 3.38d 14.25e 0.0915 [0.00254, 304 S.S-an/Polysulfone/304 S.S.an.] 122.92 1.48 25.95 @@ 0.175 [0/Poly sulfonelO] 78.27 2.20 2.34d 12.44e 0.203 [0/Polysulfone/0] 122.92 2.53 2.34d 12.44e 0.0813 [0.0813, 1100-0 Al] 136.75 2.20 41.08 27.07 0.0508 [0.0508, 5052-0 Al] 52.53 1.37 64.11d 26.88f 0.0813 [0.0813, 6061-T6AI] 226.93 2.20 68.18 27.07f 0.102 [0.102, 6061-T6 Al] 434.25 2.75 66.80d 27.07f 0.0279 [0.0279, 304 S.S.-an.] 15.23 2.24 11237d 80.26 0.0813 [0.0813, Autobody Steel] 443.00 6.34 133.05d 78.14f a Sheet thickness d (cm) [metal layers i and ii thickness (cm), metal layer i type/thermoplastic core layer type/metal layer ii type].

b Value comouted from En using m = 4d3E@.

Value computed from component layers' thicknesses and densities.

d Value obtained for same type of sheeting of different thickness.

taken from: Materials EngineeringlMaterials Selector '78, Reinhold Publishing Co., Stamford, Nov. 1977.

Taken from: Lynch, Handbook of Materials of Science, Vol. II, CRC Press, Cleveland, 1975.

As shown in the above table, a laminate (Example 59) comprised of two 0.0152 cm (0.006 inch, 6 mils) thick 6061-T6 aluminum layers laminated to each side of a 0.122 cm (0.048 inch, 48 mils) thick nylon 6,6 layer had a flexural stiffness of 606.72 :6 x 103 N/m (3465 lb./in.) [an effective flexural modulus of 27.64 x 109 N/m2 (4.01 x 106 psi)] and a weight of 2.21 kg/m2 (0.453 lb./ft.2). compared to: (a) a flexural stiffness of 443.00 ::6 x 103 N/m (2530 lb./in.) and a weight of 6.34 kg/m2 (1.3 lb./ft.2) for 0.0813 cm (0.032 inch, 32 mils) thick automobile body steel; (b) aflexural stiffness of 226.93 x 103 N/m (1296 Ib./in.) and weight of 2.20 kg/m2 (0.451 Ib./ft.2) for 0.0813 cm (0.032 inch, 32 mils) thick 6061-T6 aluminum alone; (c) a flexural stiffness of 434.25 x 1 103 N/m (2480 lb./in.) and a weight of 2.75 kg/m2 (0.564 lb./ft.2) for 0.102 cm (0.040 inch, 40 mils) thick 6061-T6 aluminum alone; and (d) a flexural stiffness of 117.84 x 103 N/m (673 lb./in.) and a weight of 2.20 kg/m2 (0.451 lb./ft.2) for 0.194 cm (0.0762 inch, 76.2 mils) thick sheet of nylon 6, 6 alone.

Thus, the laminate is 37% stiffer in flexure and 65% lower in weight per unit area than the 0.0813 cm thick steel. The laminate is more than 2.5 times stiffer in flexure than the 6061-T6 aluminum alone at equivalent weight per unit area and 37% stiffer than the 6061-T6 aluminum alone having a weight per unit area more than 20% higher than that of the laminate. And the laminate is more than five times stiffer than nylon 6, 6 alone having substantially the same weight per unit area.

It will be noted that in applications demanding relatively high flexural stiffness such as in automotive vehicle body panels and the like, a flexural stiffness of at least about 262.65 x x 103 N/m (1500 Ib./in.) is preferred, with values of at least about 437.75 x 103 N/m (2500 Ib.lin.) or higher being even more preferred.

It will be apparent, of course, that all things being equal with respect to the combination of critical service properties possessed by the laminates within the scope of the present invention, the lighter the laminate, the more desirable it becomes. In the construction industry certain applications demanding very high strength and stiffness such as in portions of some automotive vehicle bodies and in some building surfaces, steel sheeting weighing as much as 9.76 kg/m2 (2 lb./ft.2) is used. The maximum weight of the laminates of this invention is therefore about 9.76 kg/m2 (2 lb./ft.2), with values substantially below this weight being preferred.Values less than 6.34 kg/m2 (1.3 lb./ft.2), however, are more preferred, with values less than 4.88 kg/m2 (1 Ib./ft.2) still more preferred, particularly for.automobile applications. When polypropylene is the thermoplastic core and aluminum is the metal layer laminated on each side of the core, the laminates of the present invention have a maximum weight of about 5.37 kg/m2 (1.1 Ib./ft.2).

While each of the critical properties ~~ low coefficient of linear thermal expansion (less than about 63 x 10-6 C.-1), low inelastic ratio (less than about 93%) and excellentflexural stiffness (at least 52.53 x 103 N/m) is highly desirable, either taken alone is not sufficient. They must exist in combination. That is to say, in order to be broadly suitable for a wide variety and range of high performance construction applications, the metal-thermoplastic-metal laminates must have in combination a coefficient of linear thermal expansion (CLTE,) less than about63 x 0C.1, an inelastic ratio (IR,) less than about 93%, and a flexural stiffness of at least about 52.53 :6 x 103 N/m.

2. Correlation ofcriticalservice properties and thickness ratio The critical and important service properties of IR, and CLTE, (and HDT, where desired) are related to the ratio of the thicknesses of the component layers of the laminates via the product of the thickness ratio of the sum of the metal layer-thicknesses to the thermoplastic core layer thickness times the ratio of the strengths of the component layers of the laminate, that is, via the following dimensionless parameter: TR(YSm/TSc) wherein:: TR is the thickness ratio of the sum of the metal layer-thicknesses to the thermoplastic core thickness; YSm is the thickness-weight-average tensile yield strength of the two metal layers ~~ that is, the sum of the products of the thickness of each metal layer times its tensile yield strength at an offset of 5% elongation divided by the sum of the metal layers thicknesses, or in mathematical symbols, (toys + tijysii)iTm wherein: tj, tij, ys1, and ysjj are as defined hereinbelow; Tm is the sum of the metal layer-thicknesses or (tj + tis); and TSr is the tensile strength of the thermoplastic core material.

The tensile yield strength at an offset of 5% elongation for the metal layers (ys) is determined substantially in accordance with ASTM D638-72, entitled, "Standard Method of Test for Tensile Properties of Plastics".

Type I specimens are employed and the speed of testing is 5.0 mm per minute. The metal test specimens herein were pre-conditioned at 23 C. at 50% relative humidity for at least 18 hours and testing was conducted at 23 C. and 50% relative humidity. The value for ys is that of the metal after being subjected to the thermal conditions of lamination. In many cases this value for ys will not be substantially different from that of the metal before lamination since for many metals no significant change in ys occurs under typical lamination thermal conditions.In those cases where the value for ys must be determined on the metal after having been subjected to the thermal conditions of lamination, the metal could be separated from the core of the laminate for such a determination; for example, the thermoplastic core could be dissolved and the metal layers isolated for such a determination.

It is recognized that some metal layers may experience break before a strain of 5% offset. For such metals the maximum tensile strength for the material is to be used as the value for ys.

The tensile strength of the thermoplastic core material (TSC) is also determined substantially in accordance with ASTM D638-72. Type I test specimens are employed and the speed of testing is 5.0 mm per minute.

Specimens were pre-conditioned at 23"C. for at least 18 hours. All non-laminated polyamide specimens were kept dry, as molded in sealed cans with anhydrous magnesium perchlorate or anhydrous calcium sulfate desiccants during the pre-conditioning period and all other specimens were pre-conditioned at 50% relative humidity. The tensile strength of the thermoplastic materials is taken as the tensile stress at yield or in the absence of a yield point, the tensile stress at fail (break). The value for TSC is of the core after being subjected to thermal conditions of lamination which in general will be the same as the thermoplastic material before lamination. In instances where the thermoplastic is such that significant changes in TSC would likely occur during lamination, the value of TSC can be determined, for example, by subjecting a representative sample of the thermoplastic material alone to the lamination thermal conditions and taking a measurement on the resultant material.

The thickness ratio (TR) is described by the region of the numerical overlap of the parameter TR(YSm/TSC) as determined from the areas defined by the relationships of TR(YSm/TSc) to IR, (Figure 1), CLTE, (Figure 2), and, where the end-use application contemplated for the laminate requires a high heat distortion temperature, (HDT, - HDTC)/(Tm - HDTC) (Figure 3).The lower boundary of such areas is defined by the equation for a straight line: y = mx + b in which y is they-axis (vertical-axis) parameters of lR@, CLTE6, and (HDT, - HDTC)/(Tm - HDTc), xis the x-axis (horizontal-axis) parameter of TR(YSm/TSc), m is the slope of the straight line, and b is the intercept on the y-axis.

When y is IR6, m is 108 and b is zero (0) for values ofxfrom zero (0) to 0.65, and m is zero (0) and b is 70 for values of x greater than 0.65.

When y is CLTE6, m is -3.6 x 104 and b is 45 x 1 10-6 for values ofxfrom zero (0) to 0.1, and mis zero (0) and b is 9 x 10-6 for values of x greater than 0.1.

When y is (HDT6 - HDTc)/(Tmc - HDTc), m is 1 and b is zero (0) for values ofxfrom zero (0) to 0.05, m is 10 and b is -0.45 for values of x from 0.05 to to 0.12, and m is zero (0) and b is 0.75 for values of x g reater than 0.12.

The upper boundary of the areas defined by the relationships of TR(YSm/TSC) to IR, (Figure 1), CLTE, (Figure 2), and, where desired, (HDT, - HDTe)/(Trn - HDTo) is also defined by the equation for a straight line defined hereinabove for the lower boundary of such areas. When y is IR,, m is 280 and b is 30 for values ofx from zero (0) to 0.25, and m is zero (0) and b is 100 for values ofx greater than 0.25.

When y is CLTE,, m is -2.88 x 10-3 and b is 216 x 10-6 for values of xfrom zero (0) to 0.05, m is -1.29 x 10-4 and b is 78.5 x 10-6 for values of x from 0.05 to 0.26, and m is zero (0) and b is 45 x 10-6for values of x greater than 0.26.

When y is (HDT, - HDTC)/(Tm - HDTc), m is 112.5 and b is zero (0) for values ofxfrom zero (0) to 0.004, m is 15.3 and b is 0.389 for values ofxfro 0.004 to 0.04, and m is zero (0) and b is 1 for values ofx greater than 0.04.

Referring to Figure 1, it is readily seen that all of the data falls within a band defined at its outer limits by curves 1 and 2 which are, respectively.the upper and lower boundaries of the area defined by the relationship of TR(YSm/TSc) to IR6. Thus, where it is desirable to have a laminate possessing a specified inelastic ratio, IRk (less than the maximum value of 93% noted hereinabove), the thickness ratio of the laminate is readily determined by drawing a horizontal line from the desired IR, value to the point of intersection at curve 1 (and curve 2 where possible), which value(s) can be read from the TR(YSm/TSC) axis. The point of intersection at curve 1 (at IR, greater than about 30%) will establish a minimum value for the dimensionless parameter.TR itself can then be readily determined by substituting known values of YSm and TSc for chosen types of metals and thermoplastic core layers in the dimensionless parameter.

If the same horizontal line drawn to intersect curve 1 also intersects curve 2, then an upper limit for TR(YSm/TSc) as well as TR alone can also be determined in the same manner as described for the lower limits. In such an instance, a range of values for TR(YSm/TSC) and hence TR will be established. On the other hand, where the horizontal line drawn to intersect curve 1 does not also intersect curve 2, then, consistent with the thickness and weight limitations discussed hereinabove, there is no upper limit on TR(YSm/TSC).

Referring to Figure 2, it is readily seen that all of the data also falls within a band defined at its outer limits by curves 3 and 4, the upper and lower boundaries, respectively, of the area defined by the relationship of TR(YSm/TSc) to CLTE@ In a manner similar to that described for Figure 1, once a desired CLTE, (less than about 63 x 10-6 C.-1) is specified, the value (or values) for TR(YSm/TSc) and hence TR itself can be readily determined.

When heat distortion temperature of the laminates is a factor to be considered with respect to the contemplated end use application, referring to Figure 3, it is readily seen that all of the data for laminates having partly crystalline thermoplastic core layers fall within a band defined at its outer limits by curves 5 and 6which are the upper and lower boundaries, respectively, of the area defined by the relationship of TR(YSm/TSc) to (HDT, - HDTC)/(Tm - HDTc). Once a desired value for HDT, is specified, known values of HDTc and Tmc for chosen partly crystalline thermoplasticscan be substituted in the normalized HDTvariable, (HDT, - HDTc)/(Trn - HDTc) to obtain a value between zero (0.0) and 1.0.Once that value is determined, the TR(YSm/TSC) value (or values) can be determined as described for Figures 1 and 2 by drawing a horizontal line from the desired (HDT, HDTC)/(Tm5 - HDTc) value to the point of intersection at curve 5 (and curve 6, where possible).

It will be noted that the heat distortion temperature for laminates having amorphous thermoplastic core layers is substantially identical to that of the thermoplastic core layer material alone. That is to say, the lamination of metal layers on either side of an amorphous thermoplastic core layer results in little, if any, enhancement of the heat distortion temperature.

Thus, the optimum and preferred TR range for any given laminate having a specified balance of lr@ and CLTE, (and HDT, ) can be readily ascertained by correlating the TR(YSr,/TS,) values obtained from Figures 1 and 2 (and 3) and determining the region of numerical overlap of such values. In general, since the combination of low IR, and low CLTE, (and high HDT, under conditions so requiring) is preferred, a TR(YSm/TSC) within the range between about 0.08 and 0.6 is preferred, although as indicated by Figures 1 and 2 (and 3), other values also are suitable.

It will be noted, however, that regardless of the TR value, the minimum thickness of each metal layer must be at least about 0.00127 centimeter (0.0005 inch, 0.5 mils) and the maximum weight of the laminate must be no more than about 9.76 kg/m2 (2 lb./ft.2), and for the case of laminates with polypropylene as the thermoplastic core and aluminum as the metal layer on each side of the core a maximum of about 5.37 kg/m2 (1.1 Ib./ft.2). Moreover, as a practical matter, TR must be greater than zero (0) (thermoplastic alone) and less than absolute infinity (metal alone) in that the metal-thermoplastic-metal laminates within the scope of the present invention cannot be comprised of either metal or thermoplastic alone.

Once TR is determined, if a thickness is chosen for either the metal layers, Tm, or the thermoplastic core layer, the thickness for the remaining component layer is readily determined. It will be noted that in the specific instance wherein the metal layers have different compositions (that is, ysi and ysii, as defined hereinbelow, are not equal), the relative thicknesses of the metal layers must be specified in order to determine the value of YSm which in turn is required in order to calculate TR from the TR(YSm/TSC) parameter as illustrated hereinbelow.Of course, once TR is determined and since Tm (from t + tij where ti and tare the thicknesses of the respective metal layers arbitrarily labeled as "i" and "ii") is known, the required thermoplastic core layer thickness is readily determined.

The manner by which Figures 1 and 2 (and 3 when HDT, is a factor to be considered) described hereinabove are employed to establish values for TR(YSm/TSc) and hence TR alone is to choose values for the properties -- IR, and CLTE, (and HDT, when necessary) -- commensurate with the intended end use. For example, if the end use application would require an lR. of 72%, then a value for TR(YSm/TSC) ranging from about 0.15 to approximately infinity (or simply a value of at least 0.15) would be indicated by Figure 1.If the end use application would also require a CLTE, of 23.6 x 10-6 o C.-', then a TR(YSm/TSC) value ranging from about 0.065 to approximately infinity (or simply a value of at least about 0.11 ) would be indicated by Figure 2.

And if a HDT, of 158 C. would be required for the contemplated end use, choosing polypropylene (HDTc = 60 C.; Tm = 170 C.) as a partly crystalline thermoplastic core layer for illustrative purposes, the normalized HDT variable: (HDT, - HDTc)/(Tm5 - HDTc) can be readily solved [(158" C. - 600 C.) (170 C. - 60o C.)] to give a value of 0.89. This normalized HDT variable value would require, according to Figure 3, a value ranging from about 0.033 to approximately infinity (or again, simply a value of at least about 0.033).

The optimum TR(YSm/TSC) values for a laminate having an IRe of 72%, a CLTE, of 23.6 x 10-6 0 C.-l, a HDT2 of 158 C. and polypropylene as the thermoplastic core layer would be the region of overlap, namely, between 0.15 and approximately infinity (or simply a value of at least 0.15 as obtained from Figure 1).

The optimum values for TR itself can be readily determined once the metal layers ~~ for example, aluminum and more particularly the specific composition (type) and thickness of aluminum ~~ are specified.

Since: TR(YSm/TSC) = 0.15 then: TR = 0.15 (TSc/YSm) If, for illustrative purposes, 1100-0 aluminum [t = t1 = 0.0127 cm (0.000127 M, 0.005 inch, 5 mils); ysi = ys -58.25 x 106 N,m2 (8.45 x 103 lb./in.2) at an offset of 5% elongation;YSm = (tiysi + tiiysii)/Tm = [(0.000127 M x 58.25 x 106 N/m2) + (0.000127 M x 53.25 x 106 N/m2)]/0.000254M = 58.25 x 10N/M2 is chosen as the metal layers and polypropylene [(TSc = 31.71 x 106 N/m2 (4.6 x 103 Ib./in.2)], as noted hereinabove, is chosen as the thermoplastic core layer,then:

Thus, TR should have a minimum value of at least 0.0817 for the above-specified balance of IR6, CLTE,, and HDT, values for a laminate comprised of equally thick sheets of 1100-0 aluminum as the metal layers and polypropylene as the thermoplastic core layer. An experimental laminate possessing the abovespecified combination of properties with TR having the value of 0.162 is described in Example 2.

It will be noted, however, that if HDT, were not considered at all, the optimum TR(YSm/TSC) and TR values would remain unchanged since, in this instance, the region of overlap for TR(YSmlTSC) is identified solely by the values indicated by Figure 1.

On the other hand, if the region of numerical overlap for TR(YSmlTSc) is defined, in whole or in part, by the range of values indicated by Figure 3, non-consideration of HDT, in such instances would result in different values for both TR(YSm/TSc) and TR alone. For example, if an end-use application for a laminate comprised of equally thick sheets of 1100-0 aluminum [tj = tii = 0.00508 cm (0.0000508 m, 0.002 inch, 2 mils); ys = ysii = 58.25 x 106 Nlm2 at an offset of 5% elongation;YSm = (tiysi + tii tiiysii )ITm = [(0.0000508 x 58.25x 106) + (0.0000508 x 58.25'x 106)]/0.0001016= 58.25 x 106N/m2) asthemetal iayersand a block-copolymer (11.7% HYTREL 4056)-modified poly(ethylene terephthalate) (HDTc = 82 C.; Tm, = 257 C.; TSc = 58.60 x 106 N/m2) as the thermoplastlc core layer would require an IR, of 18% a CLTE, of 52.0 x 10-6 C.-1, and a HDT, of 116 C., the region of numerical overlap for TR(YSm/TSc) values as determined from Figures 1, 2 and 3 would indicate an optimum range between about 0.015 and about 0.107, and hence a TR range between about 0.0149 and about 0.106.An experimental example of such a laminate with a TR value of 0.047 is Example 96.

Disregarding HDT,, however, the region of overlap for TR(YSm/TSc) valuss as determined from Figures 1 and 2 for the above-descrlbed larninate would indlcate a slightly broadened optimum range -- that is, consistent with minimum stiffness and metal layer thickness requirements noted hereinabove, a lower limit approaching zero (0) and an upper limit of about 0.114--for TR(YSm/TSc). These values would in turn dictate a correspondingly broadened TR range, namely a lower limit approaching zero (0) and an upper limit of about 0.113.

It will be noted that since the laminates of this invention have two metal layers, one on each side of the thermoplastic core layer, the metal layers can have either the same or different compositions as long as the combination of critical and important service properties are met. Metal layers having different thicknesses also may be employed so long as such thicknesses come within the limits established by the metal layers' minimum thickness requirement and the maximum weight requirement of the resultant laminate, and the combination of critical service properties are met. When metal layers having different compositions and/or thicknesses are employed, it is preferred that certain of their important characteristics be substantially balanced in order to avoid problems such as warping, buckling, and the like when such laminates are exposed to variations in temperature.Insofar as practicable, the important characteristics of the metal layers should be balanced such that: (a) CLTEj = CLTEii; (b) tiEi = TiiEii; and (c) tjysj = t11ys1i; wherein CLTEj and CLTEii, ti and tij, Ei and Eii, and ys and ysii are, respectively, the coefficients of linear thermal expansion, thicknesses, elastic moduli, and tensile yield strengths of the respective metal layers arbitrarily labeled as "i" and "ii". However, as a practical matter, generally it is preferred that both metal layers be of the same composition and thickness.

As an example, wherein metal layers having different compositions (and different thicknesses) are employed ~~ 0.00508 cm (0.0000508 m, 0.002 inch, 2 mils) thick C 1010 low carbon steel-annealed and 0.0152 cm (0.000152 m, 0.006 inch, 6 mils) thick 6061-0 aluminum, arbitrarily labeled at ti and tij, respectively, for example ~~ and wherein for illustrative purposes, polysulfone [poly(oxy-1 ,4-phenylenesulfonyl-1 ,4- phenylene-oxy-1,4-phenyleneisopropylidene-1,4-phenylene)l is employed as the thermoplastic core layer, if the end use application would require an IR, or 33%, then a value forTR(YSm/TSc) ranging from about 0.0010 to about 0.31 would be indicated by Figure 1.If the end use application would also require a CLTE, of 29.3 x 10-6 C.-, then a TR(YSm/TSC) value ranging from about 0.043 to approximately infinity (or simply a value of at least about 0.043) would be indicated by Figure 2.

The optimum values for TR(YSmlTSC) for a laminate having an IR, of 33% and a CLTE, of 29.3 x 10-6 C.1 would be between 0.043 and 0.31, the region of numerical overlap for Figures 1 and 2.

The optimum values for TR alone can be readily determined since, as noted hereinabove, C 1010 low carbon steel-annealed (tj = 0.0000508 m; ysi = 349.53 x 106 N/m2 at an offset of 5% elongation) and 6061-0 aluminum (tii = 0.000152 m; ysii = 112.37 x 105 N/m2 at an offset of 5% elongation) are employed as the two metal layers.

Since: TR(YSm/TSC) = 0.043 to 0.31 then: TR = 0.043 (TSc/YSm) to 0.31 (TSc/YSm) The strength values (YSm and TSc) are as follows: YSm = (tjysj + tiiysii)/Tm = [(0.0000508 x 349.53 x 106)+(0.000152 x 112.37 x 106)]/0.000203 = (17756.12 + 17080.24)/0.000203=34836.36/0.000203 = 171.61 x 106 N/m2 TSc = 73.77 x 106 N/m2 Therefore,

Thus, TR should range between about 0.0185 and about 0.133 for the above-specified balance of IR6 and CLTE, values for a laminate comprised of a 0.00508cm thick sheet of C 1010 low carbon steel-annealed and a 0.0152 cm thick sheet of 6061-0 aluminum as the metal layers and polysulfone as the thermoplastic core layer.An experimental example of such a laminate having a TR value of 0.0654, with IR, measured with steel on the tension side and with CLTE, measured on the steel side is described in Example 156.

It will be noted, however, that if IR, and CLTE, were in turn measured from the aluminum side for the above-described laminate, TR(YSm/TSC) and TR would vary slightly from the above-indicated values due to the lack of an absolute balance between CLTEj and CLTE11, tjEj and tiiEu, and tjysj and tijysjj. For example, lRf as measured with the 6061-0 aluminum on the tension side had a value of 35% and CLTE, as measured from the aluminum side had a value of 37.1 x 10-6 0 C.-l. These values would require a range of TR(YSm/TSC) values between about 0.020 and about 0.33, and about 0.023 and approximately infinity as indicated, respectively, by Figures 1 and 2, with the range between 0.023 and 0.33 defining the region of numerical overlap. The value for TR alone would therefore be between about 0.00989 and about 0.142 which range correlates quite well with the TR value of 0.0654 for the laminate described in Example 156.

3. Other Important Properties In addition to the above critical construction application properties, most of the laminates within the scope of the present invention also have excellent formability at elevated temperatures, very good ductility, and high energy absorption ability.

Excellent formability is a necessary property for the laminates if they are to be formed into shaped structures subsequent to preparation; that is, subjected to post-forming operations. The excellent formability and very good ductility of the metal-thermoplastic-metal laminates prepared from ductile metal layers and a ductile thermoplastic core layer ensure that such laminates can be formed into a variety of shapes -- from slightly curved to deep drawn ~~ without failure or rupture.

The terms "ductile" and "ductility" as employed herein to describe the laminate metal and thermoplastic core layer components and the laminates within the scope of the present invention refer to such materials having a tensile elongation at break or fail of at least 10% as measured by ASTM D638-72 test method for plastics.

The forming (or, more accurately, post-forming) of the laminate can be readily accomplished by procedures known to those skilled in the art. One such procedure suitable for use herein involves subjecting the laminate to forming pressures at elevated temperatures, that is, a temperature which is sufficiently high to soften the thermoplastic core layer and permit the forming operation to be carried out without concurrent delamination, weakening of the metal layers and/orthe thermoplastic core layer, and the like. For most of the laminates of the present invention the forming operation at or near ambient temperatures is to be avoided since most of the laminates within the scope of the invention would not be expected to be cold formable at such temperatures.Herein laminates are not considered to be cold formable if at or near ambient temperature performance in a deep draw test is poor and/or the degree of bending sustainable is low and/or performance in the Olsen Cup Test is poor, such tests being further discussed hereinafter. Moreover, an additional advantage in carrying out the forming operation at elevated temperatures is that such temperatures would usually effectively destroy the ambient-temperature memory of the laminate, and thus its tendency to recover to its straightened and/or flattened configuration upon removal of the forming pressure. This loss of memory (or reset) is retained up to substantially the original forming temperatures and for some laminates even higher.As a result, at elevated temperatures laminates of the present invention prepared, for example, from ductile metal layers and a ductile thermoplastic core layer are formable into permanently shaped structures.

An important measure of the formability of the laminates within the scope of the present invention may be gained in a deep-drawing test, typical conditions for which are shown in the table below. In this test, a flat, circular sheet of laminate is forced into a female die by a male punch, to form a cup. A successful deep-draw with a high draw ratio (ratio of blank diameter to punch diameter) is desirable. Draw ratios comparable to those of drawing quality steel of equivalent stiffness are preferred. Values which are 50 percent lower than such steel are acceptable for many applications but values much lower than this would usually be considered poor.For example, as shown in the following table, a very good draw ratio between about 2.00 and about 2.31 is obtained with aluminum/nylon 6,6/aluminum or aluminum/polyester-polyether block copolymer-modified PET/aluminum laminates when the tests are conducted at temperatures between about 800 C (176 F.) and 200 C. (392 F.). This ratio is comparable to the value of about 2.4 for drawing quality steel and, in many instances, better than the value of about 2.1 for drawing quality aluminum. Laminates which have a core of nylon 6,6 and metal layers of ductile low carbon steel have been found to perform well in the deep-draw test at ambient conditions.

It will be noted, however, that the draw ratios shown in the table below are not limiting values, and therefore, even higher draw ratios for such laminates are contemplated.

Run 1 2 3 4 5 Example 26/104 26/104 26/104 63 79 Blank Diameter, cm 7.19 7.62 7.26 6.86 6.65 Blank Tempera ture, C. 180 150 150 130 150 Die Tempera ture, C. 140 150 140 130 150 Blank Holder Pressure, 0 689.40/- 689.40 689.40 1861.38 103 N/m2 1378.80 Blank Holder Temperature, "C. 140 150 150 130 150 Punch Diameter, cm 3 3b 393a 3D3a 3.3a 3.3b Punch Temperature, "C. 25 25 25 25 25 Lubricant Hydro- Hydro- Hydro- Hydro- Hydro Carbon Carbon Carbon Carbon Carbon Grease Grease Grease Grease Grease Draw Speed, cm/s 0.51 0.51 2.33 0.51 0.51 Draw Ratio 2.18 2.31 2.20 2.08 2.02 a Polished Punch b Smooth Punch Another important measure of the formability of the laminates is the degree to which they can be bent without fracture. The degree of bending sustainable by most laminates of the present invention without fracture is extremely poor at ambient temperatures and would in many cases be unsuitable for any applications requiring simple bending around even fairly large radii. Bending would be in general considered poor if the laminate would not sustain a 90" bend around a radius two times the thickness of the laminate. At elevated temperatures many of the laminates can readily be bent, without fracture, around radii sufficiently small for many applications.It should be pointed out, however, that certain laminates within the present invention have been found to have good bending capability at ambient temperature, for example, laminates which had a nylon 6,6 core and ductile low carbon steel metal layers. It would be expected that other laminates within the present invention may also perform well in bending tests at ambient conditions.

Still another test of formability is a ball punch deflection test such as the Olsen Cup Test which involves only stretch (not draw) and wherein a sheet or laminate sample is securely clamped in a ring die and stretch-formed to failure (first appearance of a fracture) with a hemispherical punch under conditions typically as shown in the table below. One measure of performance is the forming ratio [ratio of punch penetration depth (deflection) to punch diameter], with a high ratio being desirable. Using this test at low forming rates and ambient temperatures, very good forming ratios of between about 0.300 and about 0.400 have been obtained for laminates within the scope of the present invention, for example, laminates which had a nylon 6,6 core and ductile low carbon steel metal layers and other laminates as shown in the table below. These values are comparable to (and in many instances better than) the values obtained for aluminum and steel. Ratios even lower than 0.300, for example as low as 0.150, are acceptable for some applications but values much lower than this would be considered poor performance in this test.

Metal Thermoplastic Punch Diameter Deflection Forming Example Type Thicknessa, cm Type Thickness, cm cm cm Ratio 3 1100-0 Aluminum 0.0127 HDPE 0.157 5.08 1.781 0.350 5 5052-0 Aluminum 0.0127 " 0.173 5.08 1.595 0.314 6 " 0.00762 " 0.160 0.173 5.08 1.270 0.250 33 " 0.00762 Nyion 6,6 0.173 5.08 1.524b 0.300 35 " 0.0127 " 0.160 5.08 1.778 0.350 41 " 0.0127 " 0.168 5.08 1.727c 0.340 63 6061-0 Aluminum 0.0152 " 0.160 5.08 1.981c 0.390 -- Autobody Steeld 0.0838 -- -- 5.08 1.956c 0.385 -- 6061-T4 Aluminum 0.132 -- -- 5.08 1.549c 0.305 -- " 0.0813 -- -- 5.08 1.346c 0.265 -- 6061-0 Aluminum 0.0152 -- -- 5.08 1.321c 0.260 -- 5052-0 Aluminum 0.0127 -- -- 5.08 1.229c.e 0.242 -- " 0.00762 -- -- 5.08 1.321c 0.260 -- 1100-0 Aluminurn 0.0102 -- -- 5.08 1.821c 0.358 -- " 0.0127 -- -- 5.08 1.603c,e 0.316 a Thickness for each metal layer.

b Slight localized necking observed.

c Sample deflected to fracture.

d Sample taken from a 1977 Chevrolet Monte Cario hood.

e Average of two runs.

f Nose of punch was polished hard steel testing was with no lubrication between the punch and specimen punch deflection rate was about 1.27 cm./min.

Since successful deep-drawing and bending of most laminates within the scope of this invention are expected to require the use of elevated temperatures, it is decidedly advantageous for most of the laminates to carry out the forming operation at elevated temperatures, particularly for most laminates which are to be subjected to elevated temperature conditions subsequent to being formed into the desired shape. And, as noted hereinabove, laminate temperatures between about 80 C. (176 F.) and about 200 C. (392 F.) generally are suitable for carrying out post-forming operations.

It will be apparent, of course, that the laminates within the scope of the present invention, when considered with respect to the combination of critical properties which they possess as well as the excellent formability in most cases indicated by the high-draw ratio, bending, and stretching characteristics obtained in drawing, bending, and stretching tests, provide clear advantages over known laminates and other construction panel materials for use as construction panels. When compared with metals per se, the combination of critical and important service properties ~~ low coefficient of linear thermal expansion, low inelastic ratio, excellent flexural stiffness, low weight and excellent formability in most cases ~~ make the laminates even more desirable for use as construction panels.

Very good ductility at ambient temperatures is exhibited by the laminates of the present invention when both the metal layers and the thermoplastic core layer are in ductile states. It will be recognized that while it is possible to use non-ductile forms of suitable metals in which higherfiexural strength and higher effective flexural-modulus laminates are obtained, the formability discussed hereinabove is substantially reduced.

However, where shaped structures are not required or desired, and substantially flat structures are suitable, non-ductile forms of suitable metals may be employed. One measure of the ductility of the laminates may be obtained via the aforementioned Olsen Cup Test. Other measures of ductility include tensile elongation which is measured according to ASTM D 628-72 test method for plastics, and multiaxial impact strength which is measured via the Gardner Impact Strength (GIS) Test.

In the Gardner Impact Strength Test, a sheet of test specimen at least 5.08 cm by 5.08 crn (2 inches by 2 inches) in area is placed on the flat horizontal surface of a heavy steel test anvil. The specimen is centered over a vertical cylindrical hole [3.18 cm (1.25 inch) inside diameter] in the test anvil. A light-weight polished steel punch with a 1.59 cm (0.625 inch) diameter hemispherical tip is placed on the top center of the specimen. A 1.82-kg (4 Ib.) hammer is dropped from a selected height onto the punch, thereby subjecting the specimen to an impact energy in N-M (in.-lb.) determined by the product of the weight of the hammer and its initial height in cm (inches). Each laminate specimen is impacted only one time, and the formation of any crack on either side of the specimen is considered a failure for the particular impact.The test usually requires a fairly large number of test specimens (usually at least 12 to 16 for each test), and the maximum height at which more than half of the specimens pass without failure is used to calculate the GIS to within + 0.226 N-m (2 in.-lb.). From these measurements, it was determined that ductile laminates within the scope of the present invention having 20 to 30 percent less weight (mass)/m2 than 0.0813 cm thick automobile body steel show no failure at im pact energies up to at least 18.08 N-m (160 in.-lb.) and exhibit significantly smaller dents at these impacts than do the 0.0813 cm thick steel panels. Similar results are also obtained when compared with aluminum panels.Thus, the metal-thermqplastic-metal laminates also possess high energy absorption ability in that they are capable of absorbing high impact forces with little, if any, denting and, as an additional feature, any dents which do occur can be readily hammered out without damage.

The ability of the laminates within the scope of the present invention to withstand exposure to the weathering elements without deterioration of the metal-thermoplastic adhesion to the point of failure to meet the combination of critical properties' requirement is another valuable property. It will be apparent, of course, that the metal layers, if unprotected steel and the like, will corrode upon long and continuous exposure to the weathering elements. However, the adhesion between the metal layers and the thermoplastic core layer is resistant to such elements,,particularly in those instances wherein the initial metal-thermoplastic adhesion is very good. For example, little or no loss in adhesion occurs with aluminum-nylon-aluminum laminates after one month in boiling water.Further, aluminum-nylon-aluminum laminates show no loss in peel strength after 13 months in water, or after 11 months in saturated aqueous calcium chloride or sodium chloride solutions, all at ambient temperatures.

On the other hand, exposure to the weathering elements of laminates having relatively low initial metal-thermoplastic adhesion (albeit having a peel strength greater than about 1.75 x 103 N/rn (10 Ib./linear inch) as noted hereinbelow are more susceptable to partial deterioration of the adhesion as evidenced by a drop in peel strength. For example, aluminum-HDPE-aluminum laminates having a relatively low initial peel strength show up to a 50% drop in peel strength after more than 12 months in water at ambient temperatures. The metal-thermoplastic adhesion nevertheless remains sufficient to meet the combination of critical properties' requirement discussed hereinabove.

The adhesive peel strength of the layers of the laminates of the invention are not narrowly critical and can vary over wide limits. There is no particular upper limit on the peel strength since in the construction applications contemplated, the stronger the adhesion, generally the more suitable is the laminate, particularly in post-forming operations. A lower limit on peel strength of the metal layer-thermoplastic core layer adhesion, however, is much more important and generally should be greater than about 1.75 x 1 103 N/m (10 Ib./linear inch) as measured by ASTM D 903-49 (Reapproved 1972).

It will be apparent that, in addition to each of the properties enumerated and discussed hereinabove, the metal-thermoplastic-metal laminates possess smooth metal surfaces. Since, among the metals listed hereinabove as being suitable, certain of the surfaces ~~ for example, steels, iron, and the like, corrode upon continued exposure to weathering elements, it is highly advantageous to be able to easily apply a protective surface coating to such corrosion-prone metal surface and cure such protective coating so as to enhance the strength and hardness of the coating and securely adhere it to the metal surface.

Thus, the laminates ~~ shaped, as well as substantially flat ~~ are readily protected by applying conventional metal protective coatings to at least one of the metal surfaces and curing the same at elevated temperatures. As an example, since the most common of such protective coatings is paint, the metal surfaces are easily primed and painted. The paint may be cured at elevated temperatures, without the laminate undergoing any distortion, particularly when thermoplastic core layer materials having sufficiently high crystalline melting points, Tm s, (partly crystalline thermoplastics) or glass transition temperatures, T5,s, (amorphous thermoplastics), as discussed hereinbelow, are employed.For example, with respect to automobiles, curing of the paint often is carried out at temperatures as high as 163 C. (325 F.) The painted laminate is thereafter cooled to ambient temperatures. it will be recognized, however, that the actual temperature employed to cure the protective coating may vary according to the protective coating. But regardless of the actual temperature employed, whether lower or higher, it is contemplated that the protective coating will be cured at an appropriate temperature easily determined by those skilled in the art.

The laminates of this invention, when employed under conditions wherein elevated temperature conditions are encountered, must, in addition to the combination of critical and important service properties as well as other desirable properties discussed hereinabove, have a high heat distortion temperature in order to survive such conditions without buckling, warping, flattening out (if already formed into a shaped structure), and the like.As an example, when the laminates are employed as contruction panels for automotive applications, they are subjected to elevated temperature conditions extant in paint-curing ovens at least about 135 C. (27SF.). In such an instance, a heat distortion temperature (HDT, ) of at least about 135 C. is necessary with about 163 C. (325 F.) being preferred in order to provide adequate dimensional stability at even higher temperatures extant in many paint-curing ovens.

In those instances wherein a high heat distortion temperature for the laminate is desirable, the thermoplastic core layer must have either a crystalline melting point (tic) or a glass transition temperature (tug ) at least equal to, and preferably greater than, the desired heat distortion temperature. For example, for automotive applications, when a heat distortion temperature of at least about 135 C. is necessary, either Tm, or Tg must be at least 135 C. It will be noted that whereas only those polymers which are partly crystalline will have a crystalline melting point (Tm ), all polymers will possess a glass transition temperature (Tg,).

Further, since fewthermoplastics useful within the scope of the present invention (discussed hereinbelow) have sufficiently high glass transition temperatures to provide laminates having high heat distortion temperatures, it is preferred in such instances to employ partly crystalline thermoplastics having sufficiently high crystalline melting points.

The crystalline melting points of thermoplastics (Tm,) is determined by differential scanning calorimetry (DSC) using a heating rate of 10 C. per minute. The values for crystalline melting point are taken as either the temperature at which the apparent melting rate was maximum, or the temperature at which essentially the last traces of melting are detected, the latter being preferred in instances where the difference between the two is substantial, for example, greater than 10 C.

The term "partly crystalline" is employed herein to describe thermoplastic compositions, at least 40% by weight of which is organic thermoplastic polymer(s), with at least 50% by weight of the organic thermoplastic polymer(s) being polymer chains or chain segments having a degree of crystallinity (DC) greater than about 15%. The degree of crystallinity is specified by the following formula: DC = (dpc - doc)/dlooc - doc) wherein:: dpr is the density of the partly crystalline polymer chains or chain segments in the organic polymer portion of the partly crystalline thermoplastic composition at 23 C., exclusive of substantial volume fraction(s) of other non-crystallizable organic-polymer-modifier or inorganic-filler phases which the thermoplastic core compositions may contain; doc is the density of the amorphous fraction (DC = 0%) of the partly crystalline polymer chains or chain segments in the organic polymer portion of the partly crystalline thermoplastic composition at 23 C.; and d1ooc is the density of the crystalline fraction (DC = 100%) of the partly crystalline polymer chains or chain segments in the organic polymer portion of the partly crystalline thermoplastic composition at 23 C.

The value of d1ooc may be calculated from the crystal type and crystal lattice parameters obtained from wide-angle X-ray diffraction measurements. The value of doc may be obtained via density measurements on quenched samples exhibiting no apparent degree of crystallinity by X-ray diffraction or differential scanning calorimetric measurements. Alternately, the value of doc may be obtained by extrapolating the dependence of density of partly crystalline samples of the organic polymer with known finite values of apparent degree of crystallinity (DC,) to the value of density do, at which DC, is zero. Values of DC, for semi-crystalline organic polymer samples may be determined either via wide-angle X-ray diffraction, as that percent the X-radiation diffracted at wide angles by the polymer crystallites is of the total X-radiation both diffracted and scattered at wide angles by both the polymer crystallites and the amorphous portions of the polymer, or by differential scanning calorimetric measurements of the latent heat of melting, whereupon the apparent degree of crystallinity DC, is that percentage the measured head of melting is of an estimated fixed value for the perfect polymer crystal.

In a similar manner and for reasons noted hereinabove, for the thermoplastic core layer material, when a high heat distortion temperature is desired, the metals employed as the metal layers (discussed hereinbelow) must have a melting point greater than the higher of either Tm, orTg,, depending upon which is being relied upon to provide the desired heat distortion temperature. That is, when the thermoplastic core layer is partly crystalline and has a sufficiently high Tm, to yield the desired HDT6,then the metal layers must have melting points greater than the Tm, of the thermoplastic core layer.Similarly, when the thermoplastic core layer is amorphous but has a sufficiently high Tg, to yield the desired HDT" the metal layers must have melting points greater than the Tg of the thermoplastic core layer.

Surprisingly and unexpectedly, the heat distortion temperature of the laminates (HDT,) within the scope of the present invention optimally can approach essentially that of the crystalline melting point of partly crystalline thermoplastic core materials. As a result, the heat distortion temperatures of the laminates may exceed that of the thermoplastic core material by several hundred degrees when partly crystalline thermoplastic materials are employed as the thermoplastic core layer.For example, a laminate (Example 24) comprising two 0.0127 cm (0.005 inch, 5 mils) thick 1100-0 aluminum layers and a 0.295cm (0.116 inch, 116 mils) thick nylon 6,6 core layer interposed therebetween and laminated thereto had a heat distortion temperature of 228 C. (442 F.) compared to only 77 C. (171 F.) for the nylon 6,6 layer alone. Excellent dimensional stability under engineering stresses at elevated temperatures is, therefore, a highly desirable characteristic of the laminate, particularly when thermoplastic core layer materials having either high TmCs or are art employed.

It will be noted, however, that the marked increase in the heat distortion temperature shown by laminates having a partly crystalline thermoplastic core layer over that of the thermoplastic core layer alone is not shown by similar laminates having an amorphous thermoplastic core layer. For example, a laminate (Example 92) comprising two 0.0127 cm (0.005 inch, 5 mils) thick 1100-0 aluminum layers and a 0.154 cm (0.0605 inch, 60.5 mils) thick PET [poly(ethylene terephthalate)] layer having a degree of crystallinity of 38% (that is, partly crystalline) interposed therebetween and laminated thereto had a heat distortion temperature of 240 C. (464 F.) compared to only 89 C. (192 F.) for the PET alone, an increase of 151' C. (272 F.). On the other hand, a similar laminate (Example 95) comprising two 0.0127 cm (0.005 inch, 5 mils) thick 1100-0 aluminum layers and 0.168 cm (0.066 inch, 66 mils) thick amorphous PET as the thermoplastic core layer had a heat distortion temperature of only 79 C. (174 F.) as compared to 68 C. (154 F.) for the amorphous PET alone, an increase of only 11 C. (20 F.).

Heat distortion temperature, also known as deflection temperature under flexural load, is measured according to a specific modification of ASTM D 648-72 test method for plastics. In this modification, the sheet specimen width, b, is about 2.22 cm (0.875 inch), the length is about 7.62 cm (3 inches), the span between the supports is 5.08 cm (2 inches), and the maximum stress in the specimen is 1.82 x 106 N/rn2 (264 psi.) 4. Component Materials of the Laminates Materials useful as the thermoplastic core layer within the scope of the present invention are not narrowly critical. However, such thermoplastics must of necessity possess those properties and characteristics which will yield laminates having an improved combination of service properties considered important and critical for demanding construction applications.Such an important and critical combination of properties as noted hereinabove includes, among others, a coefficient of linear thermal expansion less than about 63 x 10-6 C.-', an inelastic ratio less than about 93%, and a flexural stiffness of at least about 52.53 x 103 N/rn (300 Ib./in.).

Illustrative of classes of thermoplastics suitable for use in the present invention are acetal-, acrylic-, amide-, arylene sulfide-, arylene sulfone-, arylene carbonate-, cellulosic-, ester-, imide-, olefin-, styrenic-, and vinyl-based thermoplastic polymers.

Examples of the acetal-based thermoplastics include poly(vinyl butyral), polyformaldehyde, polyacetaldehyde, copolymers and terpolymers thereof, and block-copolymer and grafted-rubber modifications thereof.

Exemplary of the acrylic-based thermoplastics are poly(methyl methacrylate) and other poly(alkylene methacrylate), poly(tert-butyl acrylate), copolymers and terpolymers thereof, vinyl, styrenic, acrylate ester and methacrylate ester copolymers and terpolymers of acrylonitrile and methacrylonitrile, and blockcopolymer and grafted-rubber modifications thereof.

The amide-based thermoplastics are exemplified by various nylons, for example, nylon 6 or poly(Ecaprolactam) or poly(imino-1-oxohexamethylene), nylon 12 or poly(lauryl lactam) or poly(12aminododecanoic acid) or poly(imino-1 -oxododecamethylene), nylon 6,6 or poly(hexamethylene adipamide) or poly(imino-adipoyliminohexamethylene), nylon 6,10 or poly(hexamethylenesebacamide) or poly(hexamethylene decanediamide) or poly(imino-hexamethyleneiminosebacoyl), nylon 6,12 or poly (hexamethylenedodecanoamide) or poly(iminohexamethyleneiminododecanedioyl), copolymers, terpolymers, block copolymers and graft copolymers thereof, and numerous partially aromatic nylons (PARNs).

PARNs result when an aromatic residue or unit is substituted in whole or in part for an aliphatic residue or unit in an aliphatic nylon polymer. For example, substitution of all of the adipic acid [HOOC-(CH2)4-COOH] residues in nylon 6,6 by those from mixtures of about 0-70% terephthalic acid (TA, or prHOOC-C6H-COOH)/ 100-30% isophthalic acid (IA, or m-HOOC-C6H6-COOH) gives suitable PARNs which are nylons 6, TA-co-6,lA or poly(hexamethylene tere-co-isophthalamides) or (poly-iminohexamethyleneiminoterephthaloyl-coisophthaloyls).Other suitable PARNs are nylons 6,6-co-6,TA, nylons 6,6-co-6,lA, nylons 6,6-co-6,TA-co-6,lA, and other similar PARNs, including PARNs wherein some or all of the diamine residues have aromatic character and those containing lactam residues, such as nylons 6-co-6,6-co-6-TA.

Other suitable amide-based thermoplastics are crystalline and amorphous nylons with branched aliphatic or cycloaliphatic diamine residues. Also suitable among the amide-based thermoplastics are blends or mixtures of the polyamides (nylons) and block and graft copolymers thereof. Examples are blends of nylon 6 with nylon 6-block-poly(tetramethylene oxide) [nylon 6-block-poly(butylene oxide)], nylon 6,6 with nylon 6-block-pol\l(propylene oxide), nylon 6,6 with poly(butyl acrylate)-graft-nylon 6,6, and many other similar blends. Such materials can exhibit low-notch sensitivity and high toughness and resistance to impact, even at low temperatures.

Illustrative of suitable ester-based thermoplastics are poly(alkylene terephthalates) having alkylene groups or residues with two to about ten carbon atoms, such as poly(ethylene terephthalate), poly(butylene terephthalate), or poly(tetramethylene terephthalate), poly(decamethylene terephthalate), poly(1 ,4- cyclohexyldimethylol terephthalate), and many similar poly(alkylene terephthalates) and poly(alkylene isophthalates) copolymers and terpolymers, and block-copolymer and grafted-rubber modifications thereof.

Exemplary of arylene ether-based thermoplastics are poly(2,6-dimethylphenylene oxide), blends with styrene-acrylonitrile (SAN) copolymers, acrylonitrile-butadiene-styrene (ABS) copolymers or resins, and block-copolymer and grafted-rubber modifications thereof.

The arylene sulfide-based thermoplastics are exemplified by poly(phenyl sulfide).

Examples of arylene sulfone-based thermoplastics are poly(oxy-l ,4-phenyienesulfonyl-1 ,4-phenyleneoxy- 1 ,4-phenyleneisopropylidene-1 ,4-phenylene) or simply polysulfone, poly(oxy-1 ,4-phenylenesulfonyl-1 ,4- phenylene) or simply polyether sulfone, and block-copolymer and grafted-rubber modifications thereof.

The cel lulosic-based thermoplastics are exemplified by cellulose acetate, cellulose propionate, cellulose butyrate, and cellulose acetate-butyrate.

Exemplary of imide-based thermoplastics are poly(N-methyl maleimide), other poly(N-alkylene maleimides), copolymers and terpolymers thereof, and block-copolymer and grafted-rubber modifications thereof, and polyimides and copoly(imide/amides) of pyromelletic dianhydride and m-phenylene diamine and other similar polyarylene imides and copoly(arlyene imide/amides).

Examples of olefin-based thermoplastics are high-density polyethylene (HDPE i.e. density greater than 0.944 gmslcm3), low-density polyethylene (LDPE i.e. maximum density of 0.944 gms/cm3) polypropylene, poly(1-butene), poly(3-methyl-butene), poly(4-methylpentene), multi-polymers derived from the corresponding monomers thereof, and block-copolymer and rubber modifications thereof. While the presently claimed invention excludes laminates which have a thermoplastic core which is high density polyethylene and aluminum laminated to both sides of said core, it is to be understood that such exclusion applies only to the homopolymer and not multi polymers derived from the corresponding monomer or block-copolymer or other modifications thereof, for example, rubber modifications and filled modifications which are discussed hereinbelow.Likewise, in claims herein the weight limitation specific to laminates having a polypropylene core and aluminum metal layers on both sides of the core applies only to that homopolymer.

The vinyl-based thermoplastics are exemplified by poly(vinyl chloride) (PVC), copolymers and terpolymers thereof, and block-copolymer, grafted-ru bber-reinforced, and ABS-resin modifications thereof.

Suitable styrenic-based thermoplastics are exemplified by copolymers containing polar functional groups such as poly(styrene-co-acrylonitrile) (SAN) and grafted-rubber modifications of SAN and its terpolymers, which modifications are ABS resins.

The thermoplastic materials can be modified with fillers, reinforcing agents, plasticizers, stabilizers, flame retardants, and other polymer modifiers, as are well-known in the art, in order to alter their properties and thereby enlarge the scope of applicability. One such modification comprises reinforcing the thermoplastic materials with mineral and/or organic fillers and fibers which may have been treated with adhesion promoters or coupling agents capable of increasing the adhesion of the fillers and fibers to the thermoplastic matrix molecules. A large number of organo-silane compounds (discussed hereinbelow) have been found to be especially capable of performing the task of improving the adhesion between thermoplastics and mineral fillers and glass fibers, thereby creating a synergistic effect when compared to non-treated fillers and fibers.

Preferred mineral fillers include small-particle-size quartz, wollastonite, feldspar, calcined kaolinite clay, and the like. The concentration of such mineral fillers, when employed, can vary from very small amounts, such as one or two percent by weight, up to about 50% by weight, or even higher, with concentrations between about 20% and about 45% by weight being preferred.

Fibers suitable for use as modifying agents include glass fibers and other high modulus, high performance fibers, such as graphite, boron, steel, aromatic-polyamide fibers, potassium titanate wiskers and the like. It will be noted that while such high modulus, high performance fibers ~~ glass fibers, for example ~~ improve the strength and flexural modulus of the thermoplastics such as herein employed, they result in a decreased multiaxial impact resistance. In spite of this apparent drawback, however, concentrations of fibers up to about 10% by weight, or even higher (such as about 33% by weight), may be advantageously employed for certain property enhancement, where desired.

Metals which are useful within the present invention are fairly wide in scope. Each metal layer must, however, have a minimum thickness of at least about 0.00127 cm (0.0005 inch, 0.5 mil). In addition, for certain specific applications such metals preferably should possess certain other properties.Such other propérties include: (a) the metals, when a high heat distortion temperature for the laminate is desired, should have a melting point greater than the higher of either the crystalline melting point or the glass transition temperature of the thermoplastic core layer, depending upon which is being relied upon to provide the desired heat distortion temperature; (b) the metals should have a tensile yield strength at an offset of 0.2% elongation greater than 1.82 x 106 N/m2 (264 IbJin.2) at temperatures greater than the higher of either Tm, of Tg, determined for such conditions substantially in accordance with ASTM D638-72 discussed hereinbefore;; (c) the metals should have a modulus of elasticity in tension greater than 34.47 x 109 N/m2 (5 x 106 psi) at ambient temperatures determined also substantially in accordance with aforementioned ASTM D638-72; and (d) the metals should be ductile, particularly when the resultant laminates are to be subjected to post-forming operations.

Metals which meet the above requirements, that is, those which result in laminates possessing the critically important combination of a coefficient of linear thermal expansion less than about 63 x 106 c an inelastic ratio less than about 93%, a flexural stiffness of at least 52.53 x 103 N/m (300 Ib./in.) and a weight less than 9.76 kg/m2 (2 lb./ft.2), may be either ferrous or non-ferrous. Exemplary of the ferrous metals are steels, particularly low-carbon steels, stainless steels, galvanized iron, and the like. Non-ferrous metals are exemplified by aluminum, magnesium, zinc, tin, nickel, titanium, copper, cobalt, beryllium, and alloys of each of these metals, such as various brasses and bronzes.

The thermoplastic core layer and the metal layers are uniformly and securely laminated together to form the laminates. If desired, a suitable adhesion agent from among those listed hereinbelow may be employed to facilitate the formation of laminates possessing the critically important properties discussed in detail hereinabove.

It will be noted that while the employment of an adhesion agent in the laminates is not essential, in general it is preferred to employ an adhesion agent to ensure strong metal-thermoplastic adhesion. For example, a peel strength of at least about 1.75 :6 x 103 N/m generally is adequate. It will be apparent, however, that even stronger metal-thermoplastic adhesion is preferred.

Adhesion agents, when employed, which are suitable for anchoring the metal layers to the thermoplastic core layer to provide adequate adhesion of the metal layers to the thermoplastic core layer are not narrowly critical. Such adhesion agents include, for example, organosilane adhesion promoters or coupling agents.

Illustrative of classes of suitable organosilane adhesion agents are amino-functional alkyltrialkoxysilanes, epoxy-functional alkytrialkoxysilanes, glycidoxy-functional alkyltrialkoxysilanes, methacryloxy-functional alkyltrialkoxysilanes, and mixtures thereof. These classes or organosilanes are exemplified, respectively by gamma-aminopropyltriethoxysilane and N-beta(aminoethyl)-gamma-aminopropyltrimethoxysilane, beta (3,4-epoxycyclohexyl )ethyltrimethoxysi lane, gamma-glycidoxypropyltrimethoxysilane, and gammamethacryloxypropyltrimethoxysilane. These compounds are commercially available from Union Carbide Corporation, New York, New York 10017 as A-1 100 silane, A-1 120 silane, A-186 silane, A-187 silane, and A-174 silane, respectively.Gamma-Glycidoxypropyltrimethoxysilane and N-beta-(aminoethyl)-gammapropyltrimethoxysilane also are commercially available from Dow Corning Corporation, Midland, Michigan, 48640 as Z6040 silane, and Z6020 silane, respectively. Such silane coupling agents may be employed as alcoholic solutions, aqueous alcoholic solutions, or simply aqueous solutions. The concentration of the silane solutions typically is between about 0.01 % and about 1.5% by weight.

Other suitable adhesion agents may also be employed. Exemplary of such other suitable adhesion agents are adhesives such as nitrile rubber-phenolic resins, epoxides, acrylonitrile-butadiene rubbers, urethane modified acrylics, polyester-co-polyamides, polyester hot melts, polyester hot melts crosslinked polyisocyanates, polyisobutylene modified styrene-butadiene rubbers, urethanes, ethylene-acrylic acid copolymers, ethylenevinyl acetate copolymers, and the like.

Of the suitable adhesion agents listed hereinabove, the organosilane adhesion promoters or coupling agents are preferred in that the resultant metal-thermoplastic adhesion in general is both stronger and more resistant to deterioration and failure.

Various techniques employing the adhesion agents noted hereinabove so as to ensure the required adhesion for the metal layer-thermoplastic core layer surfaces are suitable. One such technique gives exceptional results when the metal layers are aluminum and the thermoplastic core layer is a nylon, a nylon copolymer, a nylon terpolymer, poly(ethylene terephthalate) or modification thereof. An exemplary method employing this technique to fabricate the laminates so as to ensure strong metal-thermoplastic adhesion may be described as follows, with aluminum and nylon 6,6 being used as the metal layers and the thermoplastic layer, respectively, for convenience.The aluminum-metal layers are first subjected to a degreasing operation to remove any grease and dirt from their surfaces (although such degreasing is unnecessary, and therefore may be omitted when the metal is already free of such contaminants). For example, washing the surface or complete submersion thereof in toluene or some other suitable solvent Is convenient. If desired, the cleaned aluminum layers then may be soaked in a hot dichromate-sulfuric acid (chromic acid) solution or a dilute solution of aqueous alkali metal hydroxide ~~ for example, sodium hydroxide or potassium hydroxide ~~ to etch the surface, although said etching is not an absolute necessity.

Excess etching agent, whether hot chromic acid or dilute aqueous alkali metal hydroxide, is removed from the etched surface by thorough rinsing of such surface in water.

Following the pre-treatment (when necessary), the aluminum-metal layer surfaces are treated with an organosilane adhesion promoter to provide the preferred adhesion agent.

Alternatively, the nylon 6,6 layer similarly may be treated with an organosilane adhesion promoter. But in any event, the organosilane adhesion promoter (or in general the adhesion agent) is interposed between the facing surfaces of the aluminum layers and the nylon 6,6 layer regardless of whether it is placed on the surfaces of the aluminum layers or the surfaces of the nylon 6,6 layer.

As noted hereinabove, however, the imposition of an organosilane adhesion promoter between the facing surfaces of the metal layers and the thermoplastic layer, while convenient, is not an absolute necessity.

Other adhesion agents (or no adhesion agent at all) also can be employed, although the organosilane adhesion promoters are preferred for use as adhesion agents.

As an example, laminates comprised of aluminum as the metal layers laminated to a thermoplastic core layer of high-density polyethylene containing 10% by weight fiberglass (HDPE/10% fiberglass); aluminum laminated to low-density polyethylene (LDPE); aluminum laminated to a mineral-reinforced nylon 6-co-6,6 (VYDYNE' R-240); and aluminum laminated to a blpck copolymer (HYTREL 4056)-modified poly(ethylene terephthalate) can be prepared without utilizing any adhesion agent at all. Such laminates possess all the critical and important properties necessary for use as construction panels, even though the long-term stability of the metal-thermoplastic adhesion may suffer adversely.

It will be appreciated, however, that (when employed) the particular pre-treatment and adhesion agent, and procedure employed to provide the desired laminate will vary depending upon both the particular metal layers and the thermoplastic core layer employed and their condition.

The elevated temperatures and pressures employed in the preparation of the laminates are not narrowly critical. Suitable temperatures necessary for the formation of strong and secure metal-thermoplastic adhesion can vary, for example, between about 100 C. (212 F.) and about 350 C. (662 F.). In a similar manner, suitable pressures are those sufficient to maintain contact between the facing surfaces of the two metal layers and the thermoplastic core layer in order to permit the formation of the metal-thermoplastic adhesion having a peel strength of at least about 1.75 x 103 N/m (10 Ib./linear inch).

It will of course be appreciated that the particular conditions of temperature, pressure and the like will vary depending upon the particular materials making up the laminates.

A variety of methods of actually fabricating the laminates of the present invention may be employed, including compression molding, extrusion lamination, and the like. One preferred method of fabrication of the laminates is to extrude a sheet of the thermoplastic materials being employed and laminate the molten thermoplastic layer between the two metal layers, so as to obtain excellent adhesion as noted hereinabove.

It is also possible to cast some thermoplastics, such as nylon 6 and its block copolymers, by polymerizing e-capro-lactam by anionic polymerization in situ between the metal layers, using acyl lactams and the like such as acetylcaprolactam, adipoyl-bis-caprolactam, terephthaloyl-bis-caprolactam, isophthaloyl-biscaprolactam, and the like as initiators. It is also contemplated that the metal layers can be preformed to the desired shapes by standard metal-shaping techniques and held in a mold while the thermoplastic core layer is injection molded, compression molded, or cast polymerized between them.

5. Experimental Examples The following Examples illustrate the present invention. They are not to be construed as limitive upon the overall scope thereof. It should be understood that Examples 3-7 are not within the presently claimed invention.

Example 1 A general description of the procedures employed to prepare the metal-thermoplastic-metal laminates of this invention is given below. The procedure can be conveniently described as a step-wise procedure consisting of the following operations in the order given: (a) metal pre-treatment: (1) metal degreasing; (2) metal cleaning/etching; (b) thermoplastic pre-treatment; (c) application of the adhesion agent (if employed); (d) fabricating the laminate.

It will be noted, however, that steps (a) and/or (b) may be unnecessary and therefore may be omitted where the metal layers and/or the thermoplastic core layer materials are free from contaminating agents such as grease, dirt, and the like, for example, contemporaneously or newly extruded materials.

(a) Metal Pre-treatment - (1) Metal Degreasing - The metal surface is cleaned (when necessary) of processing oils by vapor degreasing in a suitable solvent, such as trichloroethylene. Alternatively, the surface is wiped clean with a clean cloth (a Webri I Litho Pad is convenient) while immersed in a suitable solvent, such as, for example, trichloroethylene, 1,1,1 -trichloroethane, toluene, acetone, and the like. The metal surface is thereafter rinsed with fresh solvent, either the same or different ~~ for example, an acetone rinse following an initial cleaning with toluene ~~ without wiping and the excess solvent allowed to evaporate.

(2) Metal Cleaning/Etching - Following the degreasing [Step (a)(1)] (when employed) the metal preferably is cleaned/etched prior to the application of the adhesion agent (when employed) in order to provide the highest metal-thermoplastic-adhesion strength, although in many cases the cleaning/etching is not necessary.

The metal surface can be etched by either chemical or non-chemical means. Non-chemical etching (or mechanical abrasion) includes brushing with a wire brush, grit blasting with alumina or steel grit, wet sanding, and the like. Either of these etching treatments is followed by degreasing as described in Step (a)(1).

The chemical etching media may be either alkaline, acid or some combination thereof. Suitable alkaline etching media include aqueous solutions of sodium hydroxide, sodium metasilicate, proprietary metal cleaners available commercially, such as, for example Apex 764 M cleaner (available from Apex Alkali Products Company, Philadelphia, Pennsylvania), and the like. Suitable acid etching media include dichromate-sulfuric acid (chromic acid) solutions, aqueous hydrochloric acid solutions, phosphoric acid solutions, and the like.

The particular medium employed may vary depending on the metal being used in that different metals sometimes require different treatments. In certain instances metals are suitably cleaned with several of the treatments. Exemplary treatments for specific metals include the following: (1) Aluminum (a) sodium hydroxide solution, 2-5% at 25 C.; (b) sodium metasilicate solution - 50.0 grams/liter at 70 C.; Ic) Apex 764 M cleaner - 50.0 grams/liter at 70 C.; and (d) sodium dichromate solution - 30.0 grams sodium dichromate (Na2Cr207.2H20),150 milliliters concentrated sulfuric acid (sp. gr. 1.84), and 1 liter water at 60 C.

(2) Low Carbon Steel (a) phosphoric acid, 2% at 25' C.

(3) Stainless Steel (a) Apex 764 M cleaner - 50.0 grams/liter at 70 C.; (b) wipe with 1:1 hydrochloric acid-water, abrade lightly with a wire brush, then Apex 764 M cleaner 50.0 grams/liter at 700 C.; and (c) abrade lightly with a wire brush, then Apex 764 M cleaner - 50.0 grams/liter at 70 C.

The metal surface is etched by immersing the metal in the etching medium for an appropriate time period.

Typical treatment times are: sodium hydroxide solution, 2-5 minutes; Apex 764 M cleaner and sodium metasilicate solutions, 2 minutes; dichromate-sulfuric acid (chromic acid) and phosphoric acid solutions, 5 minutes.

Following the cleaning/etching treatment, the metal is thoroughly rinsed with water. When an alkaline medium treatment is employed, in general, the metal is washed with hot, running water while wiping with a clean cloth (a Webrilt Litho Pad is convenient), followed by a hot water rinse without wiping. The metal is thereafter blown dry with a jet of clean air or nitrogen.

When an acid medium treatment is employed, in general, the metal is washed successively with tap water and demineralized water. If a silane adhesion promoter is to be applied as in Step (c), it usually is applied directly to the wet metal although it also can be applied to the dry metal, if desired. If silane is not to be used, the metal is first blown dry as described above and then oven dried at a suitably convenient temperature.

(b) Thermoplastic Pre- Treatment - In order to obtain good metal-thermoplastic adhesion during Step (d) hereinbelow, any processing aid present, for example, a mold release agent as in the case of a cast thermoplastic sheet, must be removed. If the thermoplastic is not to be used above its melting point in subsequent operations [Step (d)], its surface is prepared bythoroughly wiping with a suitable solventmoistened clean cloth, abrading lightly, again wiping the surface, and finally drying. On the other hand, if Step (d) involves melting the thermoplastic, the sanding or abrading step is not necessary unless it is to remove foreign material from the surface of the thermoplastic.

(c) Application oftheAdhesionAgent-The application method for the adhesion agent (when employed) depends on the particular system being used. When adhesion agents referred to as adhesion promoters as for example, the organosilane coupling agents are employed, they are applied as dilute solutions (usually about 0.01% to about 1.0% by weight) to the surface in question. The amount of such agent applied to the surface in question is generally quite small, and only a small amount is retained on the surface ~~ a monomolecular layer being ideal for good metal-thermoplastic adhesion. The adhesion promoters may be applied to the metal surface and/or the thermoplastic surface by immersing the surface in question into the solution or by spraying the solution onto the surface.In either case, the material is allowed to drain briefly and thereafter dried either by air drying or forced air drying with a jet of air or nitrogen without touching the silane-treated surface. An alternative method involves incorporating the adhesion promoter into the thermoplastic. However, application to the metal surface is the preferred method in that following the application, the metal can be readily baked at elevated temperatures, usually about 130 C. for between about 5 minutes and about 30 minutes, to assure complete dryness of the metal surface prior to use in Step (d).

When adhesion agents such as an epoxy or a nitrile-rubber/phenolic system is employed, they are usually applied by conventional coating techniques, for example, metering bar, roll coater, and the like. Such adhesion agents are applied in an amount such that the thickness is measured in thousandths of a centimeter (cm). They may be applied to the metal and/or the thermoplastic surface.

(d) Fabricating the Laminate Procedure (1) - Adhesion Promoter Adhesion Agent Laminate ~~ The laminates containing the organosilane adhesion promoters are fabricated by placing a layer or sheet of metal on each side of a layer of thermoplastic, with the silane-treated side of the metal layers in contact with the thermoplastic core layer.

For convenience and to avoid polymer flash getting on the hot press platens during the actual laminating phase, a "throw-away" back-up sheet is placed between the treated metal layers and the press platens. Thin gage aluminum foil is useful for this purpose. Additional back-up sheets, for example, polished metal sheets to ensure surface smoothness of the finished laminate, can also be used. The assembly is placed in a press and heated above the melting point (partly crystalline thermoplastic core) or glass transition temperature (amorphous thermoplastic core) of the polymer under sufficient pressure to maintain contact between the metal and thermoplastic and to cause the thermoplastic to flow to the thickness desired.The laminate's total thickness, in addition to the total thickness of the metal layers, is controlled by using suitable spacers between the platens, or, preferably, a TEFLON-coated metal mold frame of designated thickness around the perimeter of the laminate assembly. Contact at the desired temperature is maintained for a time sufficient to ensure good metal and thermoplastic adhesion, usually a few seconds up to about 30 minutes. The metal-thermoplastic-metal laminate is then cooled under pressure to below the melting point of the thermoplastic. The pressure is then released and the laminate removed from the press. The laminate may then be post-annealed, if desired.

Alternatively, although not generally recommended, the laminate can be removed from the press while still hot and quenched to low temperatures, for example, by quickly placing the laminate between thick cold metal plates.

Procedure (2) - Adhesive Adhesion Agent Laminate ~~ The laminates containing adhesive adhesion agents are fabricated by disposing a metal layer on each side of a thermoplastic core layer in such a manner that the adhesive adhesion agent is interposed between the facing surfaces of the metal layers and the thermoplastic core layer. The assembly is placed in a press and heated under pressure to cure the adhesive and obtain metal-thermoplastic adhesion. Generally, the assembly is not heated above the melting point of the thermoplastic. As a result, the total thickness of the fabricated laminate is determined by the sum of the total thickness of the metal layers and the thickness of the thermoplastic core layer used to prepare it.

Procedure (3) - Non-Adhesion Agent Laminate ~~ The laminates containing neither adhesion promoter nor adhesive adhesion agents are fabricated by disposing a metal layer on each side of the thermoplastic core layer in a suitable mold. The assembly is placed in a press and laminated as described in Procedure (1) above.

Procedure (4) - Continuous Extrusion Procedure ~~ The thermoplastic is extruded, in the melt between two layers of metal. Contact under pressure is maintained by pressing means such as suitably spaced, heated and/or chilled rolls and/or platens.

Alternatively, the extruded thermoplastic melt may be allowed to solidify before contact with the metal layers and then laminating as described in either of Procedures (1), (2), or (3), depending upon whether an adhesion agent is employed. Again, pressing means such as suitably spaced, heated and/or chilled rolls and/or platens are used to effect the necessary contact between the metal and thermoplastic.

Example 2 A metal-thermoplastic-metal laminate was fabricated using 0.0127 cm. (0.005 inch, 5 mils) thick 1100-0 aluminum as the metal layers and partly crystalline polypropylene as the thermoplastic core layer. The aluminum surface was degreased by immersion in toluene followed by an acetone rinse as described in Example 1 and then cleaned/etched by immersion in a 50.0 grams/liter aqueous solution of Apex 764 M (a product of Apex Alkali Products Company, Philadelphia, Pennsylvania) at 70 C. for a period of 2 minutes.

The aluminum was removed from the cleaning/etching solution and rinsed with hot, running water while wiping with a clean cloth (a Webril 9 Litho Pad is convenient) followed by a hot water rinse without wiping and thereafter blown dry with a jet of clean nitrogen. A solution containing 2.5 milliliters of hydrolyzed A-174 silane solution (prepared by agitating a mixture of 9.6 milliliters of A-174 silane, 2.5 milliliters of water, and 2 drops of glacial acetic acid at ambient temperatures to form a clear, single-phase solution) in 1000 milliliters of ethanol was applied to the cleaned/etched aluminum surface and the sheets hung vertically and allowed to drain and air dry. They were then heated in an oven at 130 C. for 5 minutes.

The polypropylene sheet surfaces were brushed with a 1% solution of dicumyl peroxide in toluene and allowed to thoroughly air dry.

The treated aluminum layers and the treated polypropylene were assembled in a 0.157 cm (0.062 inch) thick TEFLONiR'-coated stainless steel mold frame with the treated surfaces of the aluminum layers facing the treated surfaces of the polypropylene. The assembly was placed in a platen press heated to 200 C. Pressure was applied and maintained for 30 minutes after the polypropylene had flowed slightly to fill the mold cavity.

The laminate was then cooled under pressure to less than 70 C., afterwhich the pressure was released and the laminate removed from the press. The laminate's properties are tabulated in Table 1.

Example 3 A metal-thermoplastic-metal laminate was prepared using 1100-0 aluminum as the metal layers and high-density polyethylene (HDPE, available commercially from Monsanto Company, St. Louis, Missouri 63166 as MPE-210) as the thermoplastic core layer. The aluminum surface was degreased by immersion in acetone as described in Example 1 above and then cleaned/etched by immersion in a 5% aqueous solution of sodium hydroxide for a period of 5 minutes. The aluminum was removed from the alkaline solution and rinsed with hot, running water while wiping with a clean cloth (a Webriltb Litho Pad is convenient) followed by a hot water rinse without wiping and thereafter blown dry with a jet of clean nitrogen.A solution of 2.5 milliliters of hydrolyzed A-174 silane (prepared as described in Example 2 above) in 1000 milliliters of ethanol was sprayed onto the cleaned/etched aluminum surface and the sheets hung vertically to drain and air dry.

They were then heated in an oven at 1300 C. for 5 minutes.

The treated aluminum layers and the HDPE were assembled in a TEFLON'9-coated stainless steel mold frame with the treated surfaces of the aluminum layers facing the HDPE. The assembly was placed in a platen press heated to 200 C. Pressure was applied and maintained for 10 minutes after the HDPE had flowed to fill the mold cavity (approximately 3 minutes). The laminate was then cooled under pressure to less than 100" C., afterwhich the pressure was released and the laminate removed from the press. The properties of the laminate, including the component layers' thicknesses, are tabulated in Table 1.

Example 4 A 0.190cm (0.075 inch, 75 mils) thick metal-thermoplastic-metal laminate was prepared using 0.0127 cm (0.005 inch, 5 mils) thick 1100-0 aluminum as the metal layers and HDPE as the thermoplastic core layer according to the procedure described in Example 3 above except that one side of the HDPE was brushed with a 0.1% solution of benzoyl peroxide in ethanol and allowed to thoroughly air dry and the platen press was heated to 175 C. The properties of the laminate are tabulated in Table 1.

Example 5 A 0.198 cm (0.078 inch, 78 mils) thick metal-thermoplastic-metal laminate using 0.0127 cm (0.005 inch, 5 mils) thick 5052-0 aluminum as the metal layers and HDPE as the thermoplastic core layer was prepared according to the procedure described in Example 2 above except that the aluminum layers were degreased in acetone and cleaned!etched by immersion in a 5% aqueous sodium hydroxide solution at ambient temperatures for a period of 5 minutes, the dicumyl peroxide treatment was omitted, and the fabricated laminate was cooled to 100 C. before being removed from the press. The properties of the laminate are tabulated in Table 1.

Example 6 The procedure described in Example 2 above was repeated except that the aluminum surface was degreased in acetone and cleaned/etched by immersion in the aqueous solution of APEX 764 M for a period of only 1 minute, the dicumyl peroxide treatment was omitted, and the fabricated laminate was cooled to 100" C. before being removed from the press. The properties of the laminate are tabulated in Table 1.

Example 7 This Example illustrates the preparation of a metal-thermoplastic-metal laminate without subjecting the metal layers to either degreasing or cleaning/etching.

A laminate was prepared using 0.0140 cm (0.0055 inch, 5.5 mils) thick Lithoplate aluminum (Lith-Kem-Ko, wipe-on offset, brush grain) as the metal layers and HDPE as the thermoplastic core layer. The aluminum sheets were immersed in a solution containing 4 milliliters of hydrolyzed A-174 silane solution (prepared as described in Example 2 above) in 1000 milliliters of ethanol and hung vertically to drain and air dry. They were then heated in an oven at 130 C. for 30 minutes.

The HDPE surfaces were brushed with a 1% solution of cumene hydroperoxide in benzene and allowed to thoroughly air dry.

The silane-treated aluminum layers and the treated HDPE were assembled in a 0.277 cm (0.109 inch) thick TEFLOND-coated stainless steel mold frame with the treated surfaces of the aluminum layers facing the treated surfaces of the HDPE. The assembly was placed in a platen press heated to 175 C. Pressure was applied and maintained for 30 minutes after the HDPE had flowed to fill the mold cavity. The laminate was then cooled under pressure to about 100" C., afterwhich the pressure was released and the laminate removed from the press. The laminate's properties are tabulated in Table 1.

Example 8 This Example illustrates the preparation of a metal-thermoplastic-metal laminate without the use of an adhesion agent.

A 0.175 cm (0.069 inch, 69 mils) thick laminate was prepared using 0.0127cm (0.005 inch, 5 mils) thick 1100-0 aluminum as the metal layers and high-density polyethylene (HDPE) containing 10% by weight fiberglass (HDPE/10% fiberglass) as the thermoplastic core layer. The aluminum surface was degreased by immersion in 1,1,1-trichioroethane as described in Example 1 above and cleaned/etched by immersion in a sodium dichromate (chromic acid) solution containing 30.0 grams sodium dichromate dihydrate, 150 milliliters concentrated sulfuric acid (sp. gr. 1.84), and 1 liter water at 60 C. for a period of 5 minutes.The aluminum was removed from the cleaning/etching solution, rinsed thoroughly with running water followed by a demineralized water rinse, blown dry with a jet of clean nitrogen, and heated at 130 C. for 2 minutes.

The cleaned/etched aluminum and the HDPE/1 0% fiberglass were placed in a 0.150 cm (0.059 inch) thick TEFLON-coated stainless steel mold frame in a platen press heated to 216 C. A pressure of 907 kg (1 ton) or less ram force was applied for 3 minutes and thereafter increased to 13605 kg (15 tons) for 1 minute. The laminate was then cooled under pressure to 38 C., afterwhich the pressure was released and the laminate removed from the press. The laminate's properties are tabulated in Table 1.

Examples 9-10 These Examples illustrate the preparation of metal-thermoplastic-metal laminates without the use of an adhesion agent.

The laminates were prepared using 1145-0 aluminum as the metal layers and low-density polyethylene (LDPE) as the thermoplastic core layer. The aluminum surface was degreased by immersion in 1,1,1-trichioroethane as described in Example 1 above and then cleaned/etched by immersion in a sodium dichromate (chromic acid) solution containing 30.0 grams sodium dichromate dihydrate, 150 milliliters concentrated sulfuric acid (sp. gr. 1.84), and 1 liter water at 60 C. for a period of 5 minutes. The aluminum was removed from the chromic acid solution, rinsed thoroughly with running water followed by a demineralized water rinse, and blown dry with a jet of clean nitrogen. The aluminum was then heated in an oven at 130 C. for 2 minutes.

The aluminum layers, and the LDPE were assembled in a closed mold. The assembly was placed in a platen press heated to 204 C. A pressure of 1814 kg (2 tons) or less ram force was applied for 3 minutes and thereafter increased to 22675 kg (25 tons) for 1 minute. The laminate was cooled under pressure to 38 C.

afterwhich the pressure was released and the laminate removed from the press. The properties of the laminates, including the component layers' thicknesses, are tabulated in Table 1.

Examples 11- 14 The procedure described in Examples 9-10 above was repeated except that 1100-0 aluminum was employed as the metal layers. The properties of the laminates, including the component layers' thicknesses, are tabulated in Table 1.

Examples 15- 17 The procedure described in Examples 9-10 was repeated except that 5052-0 aluminum was employed as the metal layers. The properties of the laminates, including the component layers' thicknesses are tabulated in Table 1.

Example 18 A metal-thermoplastic-metal laminate using 0.0152 cm (0.006 inch, 6 mils) thick 6061-0 aluminum as the metal layers and 0.102 cm (0.040 inch) thick TEFLON-coated stainless steel mold frame, was prepared according to the procedure described in Examples 9-10. The laminate's properties are tabulated in Table 1.

Examples 19-21 These Examples illustrate the preparation of metal-thermoplastic-metal laminates without subjecting the metal layers to either degreasing or cleaning/etching.

The laminates were prepared using Lithoplate aluminum (Litho-Kem-Ko, wipe on, offset, brush grain) as the metal layers and LDPE as the thermoplastic core layer. The aluminum was immersed in a solution containing 4 milliliters of hydrolyzed A-174 silane solution (prepared as described in Example 2 above) in 1000 milliliters of ethanol and hung vertically to drain and air dry. They were then heated in an oven at 130 C. for 30 minutes.

The LDPE surfaces were brushed with a 5% solution of cumene hydroperoxide in benzene and allowed to air dry.

The treated aluminum layers and the treated LDPE were assembled in a closed mold with the treated surfaces of the aluminum layers facing the treated surfaces of the LDPE. The assembly was placed in a platen press heated to 150 C. Pressure was applied and maintained for 15 minutes after the LDPE had flowed to fill the cavity. The laminate was then cooled under pressure to 38 C., afterwhich the pressure was released and the laminate removed from the press. The laminates' properties, including the component layers' thicknesses, are tabulated in Table 1.

Example 22 A 0.155 cm (0.061 inch, 61 mils) thick metal-thermoplastic-metal laminate using 0.0152 cm (0.006 inch, 6 mils) thick 6061-T6 aluminum as the metal layers and LDPE as the thermoplastic core layer was prepared according to the procedure described in Examples 9-10 except that following the degreasing in 1,1 1-trichloroethane, the aluminum surface was sanded with 420-grit sandpaper and again degreased, and the platen press was heated to 221 C. The properties of the laminate are tabulated in Table 1.

Example 23 A metal-thermoplastic-metal laminate was prepared using 0.00508 cm (0.002 inch, 2 mils) thick 1100-0 aluminum as the metal layers and nylon 6,6 having a degree of crystallinity of 33% as the thermoplastic core layer. The aluminum surface was degreased by immersion in trichloroethylene as described in Example 1 above and then cleaned/etched by immersion in a 5% aqueous solution of sodium hydroxide at ambient temperatures for a period of 5 minutes. The aluminum was removed from the alkaline solution and rinsed with hot, running water while wiping with a clean cloth (a Febrile Litho Pad is convenient) followed by a hot water rinse without wiping and thereafter blown dry with a jet of clean nitrogen.A 0.4% aqueous solution of A-1 100 silane was applied to the cleaned/etched aluminum surface and the sheets hung vertically to drain and air dry. They were then heated in an oven at 1300 C. for thirty minutes.

The treated aluminum layers and the nylon 6,6 were assembled in a 0.178 cm (0.070 inch) thick TEFLON.coated stainless steel mold frame with the treated surfaces of the aluminum layers facing the nylon 6,6. The assembly was placed in a platen press heated to 285 C. Pressure was applied and maintained for 10 minutes after the nylon 6,6 had flowed to fill the mold cavity. The laminate was then cooled under pressure to 200 C. afterwhich the pressure was released and the laminate removed from the press. The laminate's properties are tabulated in Table 1.

Examples 24 - 30 Metal-thermoplastic-metal laminates using 1100-0 aluminum as the metal layers and nylon 6,6 as the thermoplastic core layer were prepared according to the procedure described in Example 23 above. The properties of the laminates including the component layers' thicknesses, are tabulated in Table 1.

Example 31 A 0.185 cm (0.073 inch, 73 mils) thick metal-thermoplastic-metal laminate was prepared using 0.00254 cm (.001 inch, 1 mil) thick 5052-0 aluminum sheets as the metal layers and nylon 6,6 having a degree of crystallinity of 33% as the thermoplastic core layer. The aluminum surface was degreased by immersion in toluene followed by an acetone rinse as described in Example 1 and then cleaned/etched by immersion in a 50.0 grams/liter solution of sodium metasilicate at 70" C. for a period of 2 minutes. The aluminum was removed from the solution and rinsed with hot, running water while wiping with a clean cloth (a Webril'9 Litho Pad is convenient) followed by a hot water rinse without wiping and thereafter blown dry with a jet of clean nitrogen.A solution containing 2.5 milliliters of 100 silane in 1,000 milliliters of distilled water was applied to the cleanedletched aluminum surface and the sheets hung vertically and allowed to drain and air dry.

The treated aluminum layers and the nylon 6,6 were assembled in a 0.180 cm (0.071 inch) thick TEFLON-coated stainless steel mold frame and laminated as described in Example 23 above. The laminate's properties are tabulated in Table 1.

Examples 32 - 35 Metal-thermoplastic-metal laminates using 5052-0 aluminum as the metal layers and nylon 6,6 having a degree of crystallinity of 33% as the thermoplastic core layer were fabricated according to the procedure described in Example 31 above. The laminates' properties are tabulated in Table 1.

Example 36 A metal-thermoplastic-metal laminate was fabricated using 0.00762 cm (0.003 inch, 3 mils) thick 5052-0 aluminum as the metal layers and nylon 6,6 having a degree of crystallinity of 33% as the thermoplastic core layer. The aluminum surface was degreased by immersion in 1,1,1-trichioroethane as described in Example 1 above and then cleaned/etched by immersion in a sodium dichromate (chromic acid) solution containing 30.0 grams sodium dichromate dihydrate, 150 milliliters concentrated sulfuric acid (sp. gr. 1.84), and 1 liter water at 60 C. for a period of 5 minutes. The aluminum was removed from the chromic acid solution and rinsed thoroughly with running water followed by a demineralized water rinse.A 0.4% aqueous solution of A-1100 silane in distilled water (pH adjusted to 4.0 with formic acid) was applied to the cleaned/etched surface of the wet aluminum. The aluminum sheets were blown dry with a jet of clean nitrogen and heated in an oven at 130 C. for2 minutes.

The treated aluminum layers and the nylon 6,6 were assembled in a 0.133 cm (0.0525 inch) thick TEFLON3-coated stainless steel mold frame with the treated surfaces of the aluminum layers facing the nylon 6,6. The assembly was placed in a platen press heated to 285 C. A pressure of 453.5 kg (0.5 ton) or less ram force was applied for 3 minutes and thereafter increased to 13605 kg (15 tons) for 1 minute. The laminate was then cooled under pressure to 138 C., afterwhich the pressure was released and the laminate removed from the press. The laminate's properties are tabulated in Table 1.

Examples 37-45 Metal-thermoplastic-metal laminates using 5052-0 aluminum as the metal layers and nylon 6,6 having a degree of crystallinity of 33% as the thermoplastic core layer was fabricated according to the procedure described in Example 36 above. The laminates' properties are tabulated in Table 1.

Example 46 A 0.187 cm (0.0735 inch, 73.5 mils) thick metal-thermoplastic-metal laminate was prepared using 0.00254 cm (0.001 inch, 1 mil) thick 304 stainless steel (annealed) sheets as the metal layers and nylon 6,6 having a degree of crystallinity of 33% as the thermoplastic core layer. The stainless steel surface was degreased by immersion in toluene as described in Example 1 above and then cleaned/etched by immersion in a 50.0 grams/liter solution of Apex 764 M (a product of Apex Alkali Products Company, Philadelphia, Pennsylvania) at 70 C. for a period of 2 minutes.The stainless steel was removed from the cleaning/etching solution and rinsed with hot, running water while wiping with a clean cloth (a Webrils Litho Pad is convenient) followed by a hot water rinse without wiping and thereafter blown dry with a jet of clean nitrogen. A solution containing 2.5 milliliters of All 100 silane in 1,000 milliliters of distilled water was applied to the cleaned/etched stainless steel surface and the sheets hung vertically and allowed to drain and air dry. They were then heated in an oven at 90 C. for 10 minutes.

The treated stainless steel layers and the nylon 6,6 were assembled in a 0.182 cm (0.0715 inch) thick TEFLONcoated stainless steel mold frame with the treated surfaces of the stainless steel layers facing the nylon 6,6. The assembly was placed in a platen press, heated to 285 C. Pressure was applied and maintained for 10 minutes after the nylon 6,6 had flowed to fill the mold cavity. The laminate was then cooled under pressure to 175 C., afterwhich the pressure was released and the laminate removed from the press. The laminate's properties are tabulated in Table 1.

Examples 47- 58 Metal-thermoplastic-metal laminates using 304 stainless steel (annealed) as the metal layers and nylon 6,6 having a degree of crystallinity of 33% as the thermoplastic core layer were fabricated according to the procedure described in Example 46 above. The laminates' properties are tabulated in Table 1.

Example 59 A metal-thermoplastic-metal laminate was prepared using 0.0152 cm (0.006 inch, 6 mils) thick 6061-T6 aluminum as the metal layers and nylon 6,6 having a degree of crystallinity of 33% as the thermoplastic core layer according to the procedure described in Example 23 above, except that following the degreasing step, the aluminum was sanded with wet 400-grit sandpaper and cleaned/etched in a 2.5% aqueous sodium hydroxide solution. A 0.122 cm (0.048 inch) thick TEFLON-coated stainless steel mold frame also was employed. The laminate's properties are tabulated in Table 1.

Examples 60-62 Metal-thermoplastic-metal laminates were prepared using 6061-T6 aluminum as the metal layers and nylon 6,6 having a degree of crystallinity of 33% as the thermoplastic core layer. The aluminum surface was degreased by immersion in trichloroethylene as described in Example 1 above and then cleaned/etched by immersion in a 10% aqueous hydrochloric acid solution at ambient temperatures for a period of 10 minutes.

The aluminum was removed from the cleaning/etching solution and rinsed thoroughly with running water followed by a demineralized water rinse, buffed with steel wool, and air dried. The aluminum sheets were immersed in a 0.4% aqueous solution of A-1 100 silane in distilled water and hung vertically to drain and air dry. They were then heated in an oven at 130 C. for 30 minutes.

The laminates were assembled and fabricated as described in Example 23 above. The properties of the laminates, including the component layers' thicknesses, are tabulated in Table 1.

Examples 63 - 65 Metal-thermoplastic-metal laminates using 6061-0 aluminum as the metal layers and nylon 6,6 having a degree of crystallinity of 33% as the thermoplastic core layer were prepared according to the procedure described in Example 59 above. The properties of the laminates, including the component layers' thicknesses, are tabulated in Table 1.

Examples 66- 69 These Examples illustrate the preparation of metal-thermoplastic-metal laminates without subjecting the metal layers to either degreasing or cleaning/etching.

Laminates were prepared using Lithoplate aluminum (Lith-Kem-Ko, wipe-on offset, brush grain) as the metal layers and nylon 6,6 having a degree of crystallinity of 33% as the thermoplastic core layer. The aluminum sheets were immersed in a solution containing 4 milliliters of A-1 100 silane in 1000 milliliters of 95% ethanol and hung vertically to drain and air dry. They were then heated in an oven at 130' C. for 30 minutes. The laminates were assembled and fabricated as described in Example 23 above. The properties of the laminates, including the component layers' thicknesses, are tabulated in Table 1.

Examples 70- 75 Metal-thermoplastic-metal laminates were prepared using C 1010 low carbon steel - annealed as the metal layers and nylon 6,6 having a degree of crystallinity of 33% as the thermoplastic core layer according to the procedure described in Example 23, above, except that the cleaning/etching was effected by immersion in a 2% aqueous solution of phosphoric acid at ambient temperatures for a period of 0.25 minute (15 seconds).

The laminates' properties, including the component layers' thicknesses, are tabulated in Table 1.

Examples 76- 77 These Examples illustrate the preparation of metal-thermoplastic-metal laminates having metal layers of different composition and thicknesses on each side of the thermoplastic core layer.

Example 76 ~~ A 0.284 cm (0.112 inch, 112 mils) thick laminate was prepared using 0.00508 cm (0.002 inch, 2 mils) thick 304 stainless steel (annealed) and 0.0152 cm (0.006,6 mils) thick 6061-0 aluminum as the metal layers and nylon 6,6 having a degree of crystallinity of 33% as the thermoplastic core layer. The metal layers were degreased by immersion in 1,1,1-trichloroethane as described in Example 1 above and thereafter cleaned/etched by immersion in 50.0 grams/liter aqueous solution of Apex 764 M at 70 C. for a period of 2 minutes. The metal layers were removed from the cleaning/etching solution and rinsed thoroughly with running water followed by a demineralized water rinse.A 0.3% aqueous solution of A-1 100 silane in distilled water (pH adjusted to 4.0 with formic acid) was applied to the cleaned/etched surfaces of the wet metals. The metal sheets were blown dry with a jet of clean nitrogen and heated in an oven at 130 C. for 2 minutes.

The treated metal layers and the nylon 6,6 were assembled in a 0.264 cm (0.104 inch) thick TEFLON-coated stainless steel mold frame with the treated surfaces of the metal layers facing the nylon 6,6.

The assembly was placed in a platen press heated to 285 C. A pressure of 907 kg (1 ton) or less ram force was applied for 3 minutes and thereafter increased to 13605 kg (15 tons) for 1 minute. The laminate was then cooled under pressure to 38 C., afterwhich the pressure was released, then the laminate removed from the press. The laminate's properties are tabulated in Table 1.

Example 77 ~~ A 0.279 cm (0.110 inch, 110 mils) thick metal-thermoplastic-metal laminate was prepared using 0.00508 cm (0.002 inch, 2 mils) thick 304 stainless steel (annealed) and 0.0127 cm (0.005 inch, 5 mils) thick 3003-H25 aluminum as the metal layers and nylon 6,6 having a degree of crystallinity of 33% as the thermoplastic core layer according to the procedure described in Example 76. The laminate's properties are tabulated in Table 1.

Example 78 A metal-thermoplastic-metal laminate was prepared using 0.0127 cm (0.005 inch, 5 mils) 1100-0 aluminum as the metal layers and ZYTEL'9 ST-801 (a high impact nylon 6,6) as the thermoplastic core layer according to the procedure described in Example 31, except that the aluminum was cleaned/etched in a 50.0 gram/liter aqueous solution of Apex 764 M and a 0.173 cm (0.068 inch) thick TEFLON-coated stainless steel mold frame was employed. The laminate's properties are tabulated in Table 1.

Example 79 This Example illustrates the preparation of a metal-thermoplastic-metal laminate without the use of an adhesion agent.

A 0.190 cm (0.075 inch, 75 mils) thick laminate was prepared using a 0.0127 cm (0.005 inch, 5 mils) thick 1100-0 aluminum as the metal layers and VYDYNE'9 R-240 (a Monsanto mineral reinforced nylon 6-co-6,6) as the thermoplastic core layer. The aluminum surface was degreased by immersion in 1,1,1-trichloroethane as described in Example 1 above and then cleaned/etched by immersion in a sodium dichromate (chromic acid) solution containing 30.0 grams sodium dichromate dihydrate, 150 milliliters concentrated sulfuric acid (sp.

gr. 1.84), and 1 liter water at 60 C. for a period of 5 minutes. The aluminum was removed from the cleaning/etching solution, rinsed thoroughly with running water followed by a demineralized water rinse, blown dry with a jet of clean nitrogen, and heated in an oven at 130 C. for 2 minutes.

The dry cleaned/etched aluminum layers and the VYDYNEtD R-240 were assembled in a 0.165 cm (0.065 inch) thick TEFLON'9-coated stainless steel mold frame with the cleaned/etched surfaces of the aluminum layers facing the VYDYNE R-240. The assembly was placed in a platen press heated to 285 C. A pressure of 1814 kg (2 tons) or less ram force was applied for 3 minutes and thereafter increased to 22675 kg (25 tons) for 1 minute. The laminate was then cooled under pressure to 138 C., afterwhich the pressure was released and the laminate was removed from the press. The laminate's properties are tabulated in Table 1.

Example 80 The procedure of Example 79 was repeated except that 0.0152 cm (0.006 inch, 6 mils) thick 6061-0 aluminum was used as the metal layers and a 0.160 cm (0.063 inch) thick TEFLON'-coated stainless steel mold frame was employed. The properties of the laminate are tabulated in Table 1.

Example 81 The procedure of Example 79 above was repeated, except that 0.0152 cm (0.006 inch, 6 mils) thick 6061-T6 aluminum was used as the metal layers and a 0.122cm (0.048 inch) thick TEFLON-coated stainless steel mold frame was employed. The properties of the laminate are tabulated in Table 1.

Example 82 The procedure of Example 79 above was repeated, except that 0.0127 cm (0.005 inch, 5 mils) thick 5052-0 aluminum was used as the metal layers and a 0.165cm (0.065 inch) thick TEFLON.coated stainless steel mold frame was employed. The properties of the laminate are tabulated in Table 1.

Example 83 The procedure described in Example 82 above was repeated except that a 0.152cm (0.060 inch) thick TEFLON-coated stainless steel mold frame was employed. The laminate's properties are tabulated in Table 1.

Example 84 A metal-thermoplastic-metal laminate was prepared using 0.0127 cm (0.005 inch, 5 mils) thick 5052-0 aluminum as the metal layers and a mineral reinforced nylon 6-co-6,6 (available commercially from Monsanto Company, St. Louis, Missouri 63166 as VYDYNE R-220) as the thermoplastic core layer. The aluminum surface was degreased by immersion in trichloroethylene as described in Example 1 above and then cleaned/etched by immersion in a 5% aqueous sodium hydroxide solution at ambient temperatures for a period of 5 minutes. The aluminum was removed from the alkaline solution and rinsed thoroughly with running water followed by a demineralized water rinse. A 0.4% aqueous solution of All 100 silane in distilled water was applied to the cleaned/etched surface of the wet aluminum.The aluminum sheets were blown dry with a jet of clean nitrogen and heated in an oven at 130 C. for 15 minutes.

The treated aluminum layers and the VYDYNE R-220 were assembled in a 0.168cm (0.066 inch) thick TEFLON-coated stainless steel mold frame with the treated surfaces of the aluminum facing the VYDYNE" R-220. The assembly was placed in a platen press heated to 285 C. A minimal pressure of ram force was applied for 3 minutes and thereafter increased to 22675 kg (25 tons) for 1 minute. The laminate was then cooled under pressure to 200 C. afterwhich the pressure was released and the laminate removed from the press. The properties of the laminate are tabulated in Table 1.

Example 85 A metal-thermoplastic-metal laminate was prepared using 0.00508 cm (0.002 inch, 2 mils) thick C 1010 low carbon steel-annealed as the metal layers and VYDYNEs R-240 as the thermoplastic core layer. The steel surface was degreased by immersion in 1,1,1-trichloroethane as described in Example 1 above and then cleaned/etched by immersion in a 2% aqueous solution of phosphoric acid at ambient temperatures for a period of 5 minutes. The steel was removed from the phosphoric acid solution and rinsed thoroughly with running water followed by a demineralized water rinse. A 0.2% aqueous solution of All 100 silane in distilled water (pH adjusted to 4.0 with formic acid) was applied to the cleaned/etched surface of the wet steel.The steel sheets were blown dry with a jet of clean nitrogen and heated in an oven at 130 C. for 2 minutes.

The treated steel layers and the VYDYNEd R-240 were assembled in a 0.124cm (0.049 inch) thick stainless steel TEFLON-coated mold frame with the treated surfaces of the steel facing the VYDYNE R-240. The assembly was placed in a platen press heated to 285 C. A pressure of 907 kg (1 ton) or less ram force was applied for 3 minutes and thereafter increased to 13605 kg (15 tons) for 1 minute. The laminate was then cooled under pressure to 66 C., afterwhich the pressure was released and the laminate removed from the press. The properties of the laminate are tabulated in Table 1.

Example 86 A 0.127 cm (0.050 inch, 50 mils) thick metal-thermoplastic-metal laminate was prepared using 0.00762 cm (0.003 inch, 3 mils) thick 304 stainless steel-annealed as the metal layers and VYDYNE R-240 as the thermoplastic core layer according to the procedure described in Example 85 above except that the cleaning/etching was effected by immersion in a 50.0 gram/liter aqueous solution of Apex 764 M at 70 C. for a period of 2 minutes, a 0.112 cm (0.044 inch) thick TEFLON-coated stainless steel mold frame was employed, and the fabricated laminate was cooled to 38 C. before releasing the pressure. The laminate's properties are tabulated in Table 1.

Example 87 A 0.185 cm (0.073 inch, 73 mils) thick metal-thermoplastic-metal laminate was prepared using 0.0127 cm (0.005 inch, 5 mils) thick 1100-0 aluminum as the metal layers and nylon 6,6 containing 10% by weight fiberglass as the thermoplastic core layer according to the procedure described in Example 46 above, except that the degreasing in toluene was followed by an acetone rinse, the dry A-1 100 silane-treated aluminum sheets were heated in an oven at 130 C. for 5 minutes, and a 0.160 cm (0.063 inch) thickTEFLON-coated stainless steel mold frame was employed. The properties of the laminate are tabulated in Table 1.

Example 88 A 0.193 cm (0.076 inch, 76 mils) thick metal-thermoplastic-metal laminate was prepared using 0.0127 cm (0.005 inch, 5 mils) thick 1100-0 aluminum as the metal layers and nylon 6 as the thermoplastic core layer according to the procedure described in Example 87 except that a 0.168 cm (0.066 inch) thick TEFLON-coated stainless steel mold frame was employed. The properties of the laminate are tabulated in Table 1.

Example 89 The procedure described in Example 88 was repeated except that nylon 6 containing 10% by weight fiberglass was employed as the thermoplastic core layer and a 0.157 cm (0.062 inch) thick TEFLON-coated stainless steel mold frame was employed. The properties of the laminate are tabulated in Table 1.

Example 90 A 0.234 cm (0.092 inch, 92 mils) thick metal-thermoplastic-metal laminate was prepared using 0.0127 cm (0.005 inch, 5 mils) thick 1100-0 aluminum as the metal layers and nylon 56% 6, TA-co-44% 6, IA (PARN 56/44) having a degree of crystallinity of 35% as the thermoplastic core layer according to the procedure described in Example 36 above except as follows: The treated aliminum layers and the PARN 56/44 were assembled in a 0.208 cm (0.082 inch) thick TEFLON-coated stainless steel mold frame with the treated surfaces of the aluminum layers facing the PARN 56/44. The assembly was placed in a platen press heated to 299" C. A pressure of 1814kg (2 tons) or less ram force was applied for 3 minutes and thereafter increased to 13605 kg (15 tons) for 1 minute.The laminate was then cooled under pressure to 66" C., afterwhich the pressure was released. The laminate was removed from the press and annealed at 170 C. for one hour. The properties of the laminate are tabulated in Table 1.

Example 91 This Example illustrates the use of an amorphous thermoplastic as the thermoplastic core layer.

The procedure described in Example 90 was repeated except as follows: The treated aluminum layers and the PARN 56/44 were assembled in a 0.178 cm (0.070 inch) thick TEFLO N-coated stainless steel mold frame with the treated surfaces of the aluminum layers facing the PARN 56/44. The assembly was placed in a platen press heated to 310 C. A pressure of 1814 kg (2 tons) or less ram force was applied for 3 minutes and thereafter increased to 13605 kg (15 tons) for 1 minute. The laminate was then immersed immediately in an ice-water mixture. The properties of the laminate are tabulated in Table 1.

Example 92 A 0.179 cm (0.0705 inch, 70.5 mils) thick metal-thermoplastic-metal laminate was prepared using 0.0127 cm (0.005 inch, 5 mils) thick 1100-0 aluminum as the metal layers and poly(ethylene terephthalate) (PET) having a degree of crystallinity of 38% as the thermoplastic core layer according to the procedure described in Example 36 above except as follows: The treated aluminum layers and the PET were assembled in a 0.154 cm (0.0605 inch) thick TEFLON'9-coated stainless steel mold frame with the treated surfaces of the aluminum layers facing the PET.

The assembly was placed in a platen press heated to 2400 C. A pressure of 1814 kg (2 tons) or less ram force was applied for 3 minutes and thereafter increased to 13605 kg (15 tons) for 1 minute. The laminate was then cooled under pressure to 55 C. afterwhich the pressure was released. The laminate was removed from the press and annealed at 1500 C. for 1 hour. The properties of the laminate are tabulated in Table 1.

Example 93 The procedure described in Example 92 above was repeated except that a 0.254 cm (0.100 inch) thick TEFLON-coated stainless steel mold frame was employed. The properties of the laminate are tabulated in Table 1.

Example 94 A metal-thermoplastic-metal laminate was prepared using 0.0140 cm (0.0055 inch, 5.5 mils) thick Lithoplate aluminum as the metal layers and poly(ethylene terephthalate) (PET) having a degree of crystallinity of 38% as the thermoplastic core layer. The aluminum was degreased by immersion in methylene chloride as described in Example 1 above and allowed to air dry.

A Z6020 silane solution was prepared by agitating a mixture of 11.1 grams of Z6020 silane in a solution of 3 drops of glacial acetic acid in 3.6 grams of water at ambient temperatures to form a clear, single-phase solution, which was diluted with 2254.0 grams of ethanol.

The degreased aluminum was wetted thoroughly with the above-prepared Z6020 silane solution, blown dry with a jet of clean nitrogen and heated in an oven at 100" C. for 10 minutes.

The treated aluminum layers and the PET were assembled in a 0.279cm (0.1 10 inch) thick TEFLON-coated stainless steel mold frame with the treated surfaces of the aluminum facing the PET. The assembly was placed in a platen press heated to 2820 C. A minimal pressure of ram force was applied for 3 minutes and thereafter increased to 22675 kg (25 tons) for 1 minute. The laminate was then cooled under pressure to 660 C., afterwhich the pressure was released and the laminate removed from the press. The properties of the laminate are tabulated in Table 1.

Example 95 This Example illustrates the use of an amorphous thermoplastic as the thermoplastic core layer.

The procedure described in Example 92 above was repeated except as follows: A 0.193cm (0.076 inch, 76 mils) thick metal-thermoplastic-metal laminate using 0.0127 cm (0.005 inch, 5 mils) thick 1100-0 aluminum as the metal layers and PET as the thermoplastic core layer were fabricated according to the procedures described in Example 91 above, except that the platen press temperature was 285 C. The properties of the laminate are tabulated in Table 1.

Examples 96- 103 The Examples illustrate the preparation of metal-thermoplastic-metal laminates without etching the metal layers or employing an adhesion agent.

Laminates were prepared using 1100-0 aluminum as the metal layers and a melt blend of PET having a degree of crystallinity of 38% and 11.7% poly(butylene tere-co-isophthalate)-block-poly(butylene glycol) (HYTREL 4056, available commercially from E. I. du Pont de Nemours & Co., Wilmington, Delaware 19898) as the thermoplastic core layer. The aluminum surface was degreased by immersion in trichloroethylene as described in Example 1 above, hung vertically, and allowed to air dry without dripping. The degreasing was repeated with methanol.

The degreased aluminum layers and the PET/11.7% HYTREL 4056 blend were assembled in a TEFLO N-coated stainless steel mold frame with the degreased surfaces (either metal layer surface) of the aluminum layers facing the PET/11.7% HYTRELX 4056 blend. The assembly was placed in a platen press heated to 279" C. A minimal pressure of ram force was applied for 3 minutes and thereafter increased to 22675 kg (25 tons) for 1 minute. The laminate was then cooled under pressure to 1000 C., afterwhich the pressure was released and the laminate removed from the press. The properties of the laminates, including the component layers' thicknesses, are tabulated in Table 1.

Example 104 A metal-thermoplastic-metal laminate was prepared using 0.0127 cm (0.005 inch, 5 mils) thick 1100-0 aluminum as the metal layers and PET/11.7% HYTREL 4056 as the thermoplastic core layer. The aluminum was degreased in 1,1,1-trichloroethane as described in Example 1 above, and then cleaned/etched by immersion in a 5% aqueous solution of sodium hydroxide at ambient temperatures for a period of 5 minutes.

The aluminum was removed from the alkaline solution and rinsed thoroughly with running water followed by a demineralized water rinse. A solution of 0.9985 gram of All 100 silane in 3.126 grams of water and 243.0 grams of ethanol (pH adjusted to 4.0 with formic acid) was sprayed onto the cleaned/etched surface of the wet aluminum. The aluminum sheets were blown dry with a jet of clean nitrogen and then heated in an oven at 1300 C. for 15 minutes.

The treated aluminum layers and the PET/11.7% HYTREL 4056 were assembled in a 0.150 cm (0.059 inch) thick TEFLON & coated stainless steel mold frame with the treated surfaces of the aluminum layers facing the PET/11.7% HYTREL 4056. The assembly was placed in a platen press heated to 279" C. A pressure of 2721 kg (3 tons) or less ram force was applied for 3 minutes and thereafter increased to 22675 kg (25 tons) for 1 minute. The laminate was then cooled under pressure to 52" C., afterwhich the pressure was released. The laminate was removed from the press and annealed by post-heating to 1500 C. for 20 minutes. The laminate's properties are tabulated in Table 1.

Example 105 The procedure described in Example 104 above was repeated except that a 0.165 cm (0.065 inch) thick TEFLONcoated stainless steel mold frame was employed. The laminate's properties are tabulated in Table 1.

Example 106 A metal-thermoplastic-metal laminate was fabricated using 0.0127 cm (0.005 inch, 5 mils) thick 5052-0 aluminum as the metal layers and PET/11.7% HYTREL 4056 as the thermoplastic core layer. The aluminum surface was degreased in 1,1,1-trichloroethane as described in Example 1 above and then cleaned/etched by immersion in a sodium dichromate (chromic acid) solution containing 30.0 trams sodium dichromate dihydrate, 150 milliliters concentrated sulfuric acid (sp. gr. 1.84) and 1 liter water at 60 C. for a period of 5 minutes. The aluminum was removed from the chromic acid solution and rinsed thoroughly with running water followed by a demineralized water rinse. A 0.4% aqueous solution of Z6040 silane in distilled water (pH adjusted to 4.0 with formic acid) was applied to the cleaned/etched surface of the wet aluminum. The aluminum sheets were blown dry with a jet of clean nitrogen and heated in an oven at 1300 C. for 2 minutes.

The treated aluminum layers and the PET/11.7% HYTREL 4056 were assembled in a 0.203 cm (0.080 inch) thick TEFLON'9-coated stainless steel mold frame with the treated surfaces of the aluminum layer facing the thermoplastic core layer. The assembly was placed in a platen press heated to 279"C. A pressure of 1814 kg (2 tons) or less ram force was applied for 3 minutes and thereafter increased to 22675 kg (25 tons) for 1 minute. The laminate was then cooled under pressure to 138 C., afterwhich the pressure was released and the laminate removed from the press. The laminate's properties are tabulated in Table 1.

Examples 107- 109 Metal-thermoplastic-metal laminates using 5052-0 aluminum as the metal layers and PET/11.7% HYTREL 4056 as the thermoplastic core layer were prepared according to the procedure described in Example 106 above. The properties of the laminates including the component layers' thicknesses, are tabulated in Table 1.

Examples 110- 113 Metal-thermoplastic-metal laminates were prepared using 6061-0 aluminum as the metal layers and a melt blend of PET/11.7% HYTREL 4056 as the thermoplastic core layer. The aluminum surface was degreased by immersion in trichloroethylene followed by an acetone rinse as described in Example 1 above and then cleaned/etched by immersion in a 2.5% aqueous sodium hydroxide solution at ambient temperatures for a period of 5 minutes. The aluminum was removed from the alkaline solution and rinsed thoroughly with running water followed by a demineralized water rinse.The wet aluminum was immersed in a mixture of 50 milliliters of A-1 100 silane solution (prepared by mixing 0.83 gram of 100 silane with 208.0 grams of water) and 50 milliliters of A-174 silane solution (prepared by agitating a mixture of 10.0 grams of A-1 74 silane, 2.5 grams of water, and 0.04 gram of glacial acetic acid at ambient temperatures to form a clear, single-phase solution, and diluting with 2449.0 grams of water, and 10 milliliters of ethanol), blown dry with a jet of clean nitrogen and heated in an oven at 1300 C. for 2 minutes.

The treated aluminum layers and the PET/11/7% HYTRELX 4056 were assembled in a TEFLON-coated stainless steel mold frame with the treated surfaces of the aluminum facing the PET/1 1.7% HYTRELss 4056.

The assembly was placed in a platen press heated to 279" C. A minimial pressure of ram force was applied for 3 minutes and thereafter increased to 22675 kg (25 tons) for an additional 3 minutes. The laminate was then cooled under pressure to 660 C., afterwhich the pressure was released and the laminate removed from the press. The properties of the laminates, including the component layers' thicknesses, are tabulated in Table 1.

Examples 114- 116 The procedure described in Examples 110-113 above was repeated except that 6061-T6 aluminum was used as the metal layers and ethanol was omitted from the A-1 74 silane solution. The properties of the laminates, including the component layers' thicknesses, are tabulated in Table 1.

Example 117 The procedure described in Example 94 above was repeated except that a melt blend of PET/11.7% HYTREL 4056 was employed as the thermoplastic core layer. The properties of the laminate are tabulated in Table 1.

Example 118 A 0.127 cm (0.050 inch, 50 mils) thick metal-thermoplastic-metal laminate using 0.00508 cm (0.002 inch, 2 mils) thick C 1010 low carbon steel-annealed as the metal layers and PET/11.7% HYTRELD 4056 as the thermoplastic core layer was prepared according to the procedure described in Example 85 above except that the steel layers were immersed in the phosporic acid solution for 2 minutes, a 0.117 cm (0.046 inch) thick TEFLON-coated stainless steel mold frame was employed, and the fabricated laminate was cooled to 38 C.

before being removed from the press. The laminate's properties are tabulated in Table 1.

Example 119 The procedure described in Example 118 was repeated except that 0.208 cm (0.082 inch) thick TEFLONs-coated stainless steel mold frame was employed. The laminate's properties are tabulated in Table 1.

Example 120 A metal-thermoplastic-metal laminate was prepared using 0.0127 cm (0.005 inch, 5 mils) thick 1100-0 aluminum as the metal layers and a melt blend of of PET having a degree of crystallinity of 38% and 11.1% poly(ethylene terephthalate)-b/ock-45% poly(butylene oxide) (PETBCP), with the poly(butylene oxide) blocks having a molecular weight of 1000, as the thermoplastic core layer. The aluminum was degreased by immersion in methylene chloride as described in Example 1 above and allowed to air dry.The aluminum was immersed in an equivolume solution (50 milliliters each) of A-1 100 silane solution (prepared by mixing 10.6 milliliters of A-1 100 silane and 31.3 milliliters of water with 3095 milliliters of ethanol) and A-174 silane solution (prepared by agitating a mixture of 9.6 milliliters of A-174 silane, 2.5 milliliters of water, and 2 drops of glacial acetic acid at ambient temperatures for 30 minutes for form a clear, single-phase solution and diluting with 3120 milliliters of ethanol), blown dry with a jet of clean nitrogen and heated in an oven at 1300 C. for 2 minutes.

The treated aluminum layers and the PET/1 1.1% PETBCP were assembled in a 0.282 cm (0.111 inch) thick TEFLON'-coated stainless steel mold frame and laminated as described in Examples 110-113 above. The laminate's properties are tabulated in Table 1.

Examples 121- 124 Metal-thermoplastic-metal laminates using 6061-0 aluminum as the metal layers and a melt blend of PET/11.1% PETBCP as the thermoplastic core layer were prepared according to the procedure described in Examples 110-113 except that the acetone rinse was omitted in the degreasing step. The properties of the laminates, including the component layers' thicknesses, are tabulated in Table 1.

Example 125 A metal-thermoplastic-metal laminate was prepared using 0.0152 cm (0.006 inch, 6 mils) thick 6061-T6 aluminum as the metal layers and a melt blend of PET/11.1% PETBCP as the thermoplastic core layer was prepared as described in Examples 121-124 except that following the degreasing, the aluminum was wet sanded with 400-grit sandpaper prior to being etched in the 2.5% aqueous sodium hydroxide solution. The properties of the laminate are tabulated in Table 1.

Example 126 A metal-thermoplastic-metal laminate using 0.0127 cm (0.005 inch, 5 mils) thick aluminum as the metal layers and partly crystalline poly(ethylene terephthalate)-block-5% poly(butylene oxide) (PET-b-5% PBO), with the PBO block having a molecular weight of 1000, as the thermoplastic core layer was prepared according to the procedure described in Example 36 above. The laminate's properties are tabulated in Table 1.

Example 127 This Example illustrates the preparation of a metal-thermoplastic-metal laminate without etching the metal or using an adhesion agent.

A laminate was prepared using 0.0127 cm (0.005 inch, 5 mils) thick 1100-0 aluminum as the metal layers and partly crystalline poly(ethylene terephthalate)-block-24% poly(butylene oxide) (PET-b-24% PBO), with the PBO blocks having a molecular weight of 1000 as the thermoplastic core layer. The aluminum was degreased by immersion in methylene chloride as described in Example 1 above and allowed to air dry. The degreased aluminum layers and the PET-b-24% PBO were assembled in a 0.292 cm (0.115 inch) thick TEFLON-coated stainless steel mold frame with the degreased surfaces (either surface) facing the PET-b-24% PBO. The assembly was placed in a platen press heated to 282 C.A minimal pressure of ram force was applied for 3 minutes and thereafter increased to 22675 kg (25 tons) for an additional 3 minutes.

The laminate was then cooled under pressure to 66 C., afterwhich the pressure was released and the laminate removed from the press. The properties of the laminate are tabulated in Table 1.

Examples 128- 131 Metal-thermoplastic-metal laminates using 1100-0 aluminum as the metal layers and a melt blend of poly(ethylene terephthalate) (PET) having a degree of crystallinity of 38% and 23.5% HYTREL 4056 as the thermoplastic core layer were prepared according to the procedure described in Examples 110-113 except that methylene chloride was employed as the degreasing solvent and the cleaning/etching of the aluminum surface was effected by immersion in a 5% aqueous sodium hydroxide solution at ambient temperatures for a period of 10 minutes. The properties of the laminates are tabulated in Table 1.

Example 132 The procedure described in Example 94 above was repeated except that a melt blend of PET having a degree of crystallinity of 38% and 23.5% HYTREL' 4056 was employed as the thermoplastic core layer. The laminate's properties are tabulated in Table 1.

Example 133 The procedure described in Example 91 above was repeated, except that a melt blend of PET having a degree of crystallinity of 38% and 10% poly(oxycarbonyloxy-1 ,4-phenyleneisopropylidene-1 ,4-phenylene) also known as poly[2,2-bis(4'-phenylene)propane carbonate] or simply polycarbonate of PC, available commercially as MERLON M100 from Mobay Chemical Corp., Pittsburgh, Pennsylvania 15205) was employed as the thermoplastic core layer and a 0.183cm (0.072 inch) thick TEFLON'-coated stainless steel mold frame was employed. The laminate's properties are tabulated in Table 1.

Example 134 A 0.190cm (0.075 inch, 75 mils) thick metal-thermoplastic-metal laminate using 0.0127 cm (0.005 inch, 5 mils) thick 1100-0 aluminum as the metal layers and poly(ethylene 80% terephthalate-co-20% isophthalate) (PET/I 80/20) having a degree of crystallinity of 32% as the thermoplastic core layer, and a 0.4% aqueous solution of A-1 100 silane in distilled water (pH adjusted to 4.0 with formic acid) as the adhesion agent was prepared according to the procedure described in Example 106 above except as follows: The treated aluminum layers, and the PET/I 80/20 were assembled in a 0.165 cm (0.065 inch) thick TEFLON-coated stainless steel mold frame with the treated surfaces of the aluminum layers facing the PET/I 80/20.The assembly was placed in a platen press heated to 240 C. A pressure of 1814 kg (2 tons) or less ram force was applied for 3 minutes and thereafter increased to 13605 kg (15 tons) for 1 minute. The laminate was then slow-cooled under pressure to 54" C., afterwhich the pressure was released and the laminate removed from the press. The laminates' properties are tabulated in Table 1.

Example 135 The procedure described in Example 91 above was repeated except that the amorphous PET/I 80/20 having a degree of crystallinity of only 5% was used as the thermoplastic core layer, a 0.170 cm (0.067 inch) thick TEFLON-coated stainless steel mold frame was employed, and the platen press was heated to 285 C. The properties of the laminates are tabulated in Table 1.

Example 136 The procedure described in Example 135 above was repeated except that the amorphous PET/I 80/20 had a degree of crystallinity of only 3.3% and a 0.142 cm (0.056 inch) thick TEFLON-coated stainless steel mold frame was employed. The properties of the laminate are tabulated in Table 1.

Example 137 A metal-thermoplastic-metal laminate was prepared using 0.0127cm (0.005 inch, 5 mils) thick 1100-0 aluminum as the metal layers and a partly crystalline melt blend of poly(ethylene 80% terephthalate-co-20% isophthalate) (PET/I 80/20) and 11.7% HYTREL 4056 as the thermoplastic core layer. The aluminum surface was degreased by immersion in methylene chloride as described in Example 1 above and allowed to air dry.

The degreased aluminum was immersed in a 0.4% solution of Z6020 silane in ethanol (prepared as described in Example 94 above), blown dry with a jet of clean nitrogen and heated in an oven at 100 C. for 10 minutes.

The treated aluminum layers and the PET/I 80/20/11.7% HYTREL's 4056 were assembled in a 0.282 cm (0.111 inch) th ick TEFLON-coated stai nless steel mold frame with the treated su rfaces of the alu minum facing the PET/I 80/20/11.7% HYTRELs 4056. The assembly was placed in a platen press heated to 249 C. A minimal pressure of ram force was applied for 3 minutes and thereafter increased to 22675 kg (25 tons) for an additional 3 minutes. The laminate was then cooled under pressure to 66" C., afterwhich the pressure was released and the laminate removed from the press. The laminate was annealed by melting to 1500 C. for 20 minutes. The properties of the laminate are tabulated in Table 1.

Example 138 The procedure described in Example 137 above was repeated except that 0.0140 cm (0.0055 inch, 5.5 mils) thick Lithoplate aluminum was employed as the metal layers and a 0.279 cm (0.110 inch) thick TEFLON R -coated stainless steel mold frame was employed. The laminate's properties are tabulated in Table 1.

Example 139 The procedure described in Example 134 was employed except that poly(butylene terephthalate) (PBT) was employed as the thermoplastic core layer and a 0.165 cm (0.065 inch) thick TEFLON i-coated stainless steel mold frame was employed. The properties of the laminate are tabulated in Table 1.

Example 140 The procedure described in Example 139 using a 0.282 cm (0.111 inch) thick TEFLON9-coated stainless steel mold frame was employed. The laminate's properties are tabulated in Table 1.

Example 141 The procedure described in Example 94 above was employed except that partly crystalline poly(butylene terephthalate) (PBT, available commercially as VALOR 310 from General Electric Company, Pittsfield, Massachusetts 01201) was employed as the thermoplastic core layer and the press platens were heated to 252 C. The laminate's properties are tabulated in Table 1.

Example 142 The procedure described in Example 137 above was repeated except that a partly crystalline melt blend of PBT and 11.7% HYTRELs 4056 (PBT/1 1.7% HYTRELd 4056) was employed as the thermoplastic core layer.

The laminate's properties are tabulated in Table 1.

Example 143 The procedure described in Example 142 above was repeated except that 0.0140 cm (0.0055 inch, 5.5 mils) thick Lithoplate aluminum was employed as the metal layers. The laminate's properties are tabulated in Table 1.

Example 144 The procedure described in Example 141 was repeated except that 0.0127 cm (0.005 inch, 5 mils) thick 1100-0 aluminum was employed as the metal layers, a partly crystalline melt blend of PBT and 23.5% HYTREL 4056 (PBT/23.5% HYTREL 4056) was employed as the thermoplastic core layer, and a 0.274 cm (0.108 inch) thickTEFLONcoated stainless steel mold frame was employed. The laminate's properties are tabulated in Table 1.

Example 145 The procedure described in Example 144 above was employed except that 0.0140 cm (0.0055 inch, 5.5 mils) thick Lithoplate aluminum was employed as the metal layers and a 0.277 cm (0.109 inch) thick TEFLON'-coated stainless steel mold frame was employed. The laminate's properties are tabulated in Table 1.

Example 146 A 0.211 cm (0.83 inch, 83 mils) thick laminate using 0.0127 cm (0.005 inch, 5 mils) thick 1100-0 aluminum as the metal layers and HYTRELe 7246 as the thermoplastic core layer was prepared according to the procedure described in Example 36 above, except that the initial applied pressure was 1814kg (2 tons) or less ram force and the fabricated laminate was cooled to 54 C. before being removed from the press. The properties of the laminate are tabulated in Table 1.

Example 147 The procedure described in Examples 128-131 was employed except that a partly crystalline poly(butylene terephthalate-co-isophthalate)-b/ock-poly(butylene oxide) (HYTREL 7246) was employed as the thermoplastic core layer and a 0.282 cm (0.111 inch) thick TEFLON-coated stainless steel mold frame was employed. The laminate's properties are tabulated in Table 1.

Example 148 A metal-thermoplastic-metal laminate was prepared according to the procedure described in Example 94 above except that HYTRELR' 7246 was employed as the thermoplastic core layer. The properties of the laminate are tabulated in Table 1.

Example 149 A metal-thermoplastic-metal laminate was prepared according to the procedure described in Example 94 above, except that a partly crystalline poly(butylene terephthalate-co-isophthalate)-b/ock-poly(butylene oxide) (HYTREL & 6346) was employed as the thermoplastic core layer. The properties of the laminate are tabulated in Table 1.

Example 150 A metal-thermoplastic-metal laminate was prepared according to the procedure described in Example 141 above except that a partly crystalline poly(butylene terephthalate-co-isophthalate)-block-poly(butylene oxide) (HYTREL 5555) was employed as the thermoplastic core layer and a 0.264 cm (0.104 inch) thick TEFLON-coated stainless steel mold frame was employed. The properties of the laminate are tabulated in Table 1.

Example 151 The procedure described in Example 141 was employed except that a partly crystalline poly(butylene terephthalate-co-isophthalate)-b/ock-poly(butylene oxide) (HYTREL 4055) was employed as the thermoplastic core layer. The properties of the laminate are tabulated in Table 1.

Example 152 A metal-thermoplastic-metal laminate was prepared using 0.0127 cm (0.005 inch, 5 mils) thick 1100-0 aluminum as the metal layers and poly(oxycarbonyloxy-1,4-phenyleneisopropylidene-1,4-phenylene) (also known as poly[2,2-bis(4'-phenylene) propane carbonate] or simply polycarbonate, available commercially as LEXAN R from General Electric Company, Pittsfield, Massachusetts 01201) as the thermoplastic core layer.

The aluminum surface was degreased by immersion in toluene followed by an acetone rinse as described in Example 1 above and cleaned/etched by immersion in 5% aqueous sodium hydroxide at ambient temperatures for a period of 2 minutes. The aluminum was removed from the cleaning/etching solution, rinsed with hot running water while wiping with a clean cloth (a Webril'8 Litho Pad is convenient) followed by a hot water rinse without wiping, and thereafter blown dry with a jet of clean nitrogen. A solution of 2.5 milliliters of A-1 100 silane in 1000 milliliters of water was sprayed onto the cleaned/etched surface and the sheets hung vertically to drain and air dry.

The polycarbonate was washed with acetone, sanded with 400-grit sandpaper, washed again with acetone, and dried overnight, (approximately 16 hours) at 60 C. in a nitrogen-purged vacuum oven.

The treated aluminum layers and the treated polycarbonate were assembled in a 0.122 cm (0.048 inch) thick TEFLON R -coated stainless steel mold frame with the treated surfaces of the aluminum layers facing the treated surfaces of the polycarbonate. The assembly was placed in a platen press, heated to 230 C. Pressure was applied and maintained for 20 minutes after the polycarbonate had flowed to fill the mold cavity. The laminate was then cooled to less than 70 C., afterwhich the pressure was released and the laminate removed from the press. The laminates' properties are tabulated in Table 1.

Example 153 A metal-thermoplastic-metal laminate using 0.0127 cm (0.005 inch, 5 mils) thick 1100-0 aluminum as the metal layers and acrylonitrile-butadiene-styrene (ABS) copolymer as the thermoplastic core layer was prepared according to the procedure described in Example 152 above, except that a solution of 2.5 milliliters of hydrolyzed A-187 silane (prepared by agitating 10.0 grams of A-187 silane, 2.3 grams of water, and 2 drops of glacial acetic acid at ambient temperatures for 30 minutes to form a clear, single-phase solution) in 1000 milliliters of ethanol was employed as the adhesion agent, a 0.190 cm (0.075 inch) thick TEFLON Rl-coated stainless steel mold frame was employed to gage the thermoplastic core layer thickness, and the platen press was heated to a temperature of 200 C.The laminate's properties are tabulated in Table 1.

Example 154 The procedure described in Example 153 above was repeated except that poly(vinyl chloride) was used as the thermoplastic core layer and a 0.147 cm (0.058 inch) thick TEFLON-coated stainless steel mold frame was employed to gage the thickness thereof. The properties of the laminate are tabulated in Table 1.

Example 155 A metal-thermoplastic-metal laminate was prepared using 0.00254 cm (0.001 inch, 1 mil) thick 304 stainless steel-annealed as the metal layers and poly(oxy-1 ,4-phenylenesulfonyl-1 ,4-phenyleneoxy-1 ,4- phenyleneisopropylidene-1,4-phenylene) (polysulfone, available commercially from Union Carbide Corporation, New York, New York 10017) as the thermoplastic core layer. The aluminum surface was degreased by immersion in 1,1,1 -trichloroethane as described in Example 1 above and then cleaned/etched by immersion in a 50.0 gramiliter aqueous solution of Apex 764 M at 70 C. for a period of 2 minutes. The steel was removed from the cleaning/etching solution and rinsed thoroughly with running water followed by a demineralized water rinse.A 0.3% aqueous solution of A-1 100 silane in distilled water (pH adjusted to 4.0 with formic acid) was sprayed onto the cleaned/etched surface of the wet steel. The steel sheets were blown dry with a jet of clean nitrogen and heated in an oven at 130 C. for 2 minutes.

The treated steel layers and the polysulfone were assembled in a 0.0864 cm (0.034 inch) thick TEFLON-coated stainless steel mold frame with the treated surfaces of the steel facing the polysulfone. The assembly was placed in a platen press, heated to 329 C. A pressure of 907 kg (1 ton) or less ram force was applied for 3 minutes and thereafter increased to 13605 (15 tons) for 1 minute. The laminate was then cooled under pressure to 66 C., afterwhich the pressure was released and the laminate removed from the press.

The properties of the laminates are tabulated in Table 1.

Examples 156- 157 These Examples illustrate the preparation of metal-thermoplastic-metal laminates having different metal layer compositions on each side of the thermoplastic core layer.

Example 156 A laminate using 0.00508 cm (0.002 inch, 2 mils) thick C 1010 low carbon steel annealed and 0.0152 cm (0.006 inch, 6 mils) 6061-0 aluminum as the metal layers and polysulfone as the thermoplastic core layer was prepared according to the procedure described in Example 155 above except that a 0.310 cm (0.122 inch) thick TEFLON -coated stainless steel mold frame was employed. The properties of the laminate are tabulated in Table 1.

Example 157 A laminate using 0.00508 cm (0.002 inch, 2 mils) thick C 1010 low carbon steel-annealed and 0.0140 cm (0.0055 inch, 5.5 mils) thick 3003-H25 aluminum as the metal layers and polysulfone as the thermoplastic core layer was prepared according to the procedure described in Example 156 above except that 0.311 cm (0.1225 inch) thick TEFLON R'-coated-stainless steel mold frame was employed. The properties of the laminate are tabulated in Table 1.

Examples 158- 161 These Examples illustrate the fabrication of metal-thermoplastic-metal laminates by polymerization of monomeric materials in situ between the metal layers. The properties of the laminates are tabulated in Table 1.

The laminates were prepared using 0.0127 cm (0.005 inch, 5 mils) thick aluminum as the metal layers. The aluminum surface was degreased by immersion in toluene followed by an acetone rinse as described in Example 1 above and then cleaned/etched by immersion in 5% aqueous sodium hydroxide at ambient temperatures for a period of 2 minutes. The aluminum was removed from the alkaline solution and rinsed for 10 minutes with running water followed by a demineralized water rinse. A 0.4% solution of A-1 100 silane in ethanol was sprayed into the cleaned/etched surface of the wet aluminum. The aluminum sheets were blown dry with a jet of clean nitrogen and heated in an oven at 130 C. for 30 minutes.

Example 15S ~~ A laminate was prepared in situ by polymerization of a nylon 6 block copolymer between Lithoplate aluminum layers. A solution was prepared containing 6.0 grams of VORANOLD 2120 (polyoxypropylene diol with hydroxyl number of 56.8), 14.4 grams of isophthaloyl-bis-caprolactam, 1.5 grams of FLECTOL"' H (polymerized 1 ,2-dihydro-2,2,4-trimethylquinoline), and 109.0 grams of E-caprolactam.

The solution was dried by distilling 25 milliliters of caprolactam under reduced pressure. A separate catalyst solution was prepared by adding 7 milliliters of 3 molar ethylmagnesium bromide in diethyl ether to 175.0 grams of dry molten E-caprolactam at 1000 C. The solution was evacuated to remove ether and ethane and held at 100" C. under nitrogen until just prior to use.

A mold was prepared by placing the two aluminum sheets between heated platens in a closed press such that the treated surfaces would face the polymerized thermoplastic. The aluminum sheets were separated by 0.318 cm (0.125 inch) thick TEFLON spacers. With the mold and reactive solutions at 1300 C the solutions were pump cast into the mold using Zenith gear pumps. The stream volume ratio of monomer solution to catalyst solution was 1.12:1. The streams were mixed by meansof a Kenics static mixer. After 5 minutes in the mold, the laminate was removed and allowed to cool. The nylon 6 block copolymer contained 20% by weight polyoxypropylene blocks.

Example 159 ~~ A laminate was made similar to Example 158 above except that 1100-0 was employed as the metal layers.

Example 160 ~~ A nylon 6 laminate was prepared by polymerizing E-caprolactam between 1100-0 aluminum layers. The mold was prepared as described in Example 158 above. A solution was prepared containing 350.0 grams of molten E-caprolactam 1.5 grams of FLECTOL H and 3.4 grams of PEI-1000 (polyethylenimine, 30% aqueous solution). The solution was dried by distilling 50 milliliters of caprolactam at reduced pressure.

The solution was catalyzed by the addition of 6.2 milliliters of 3 molar ethylmagnesium bromide in diethyl ether, followed by thorough degassing under vacuum. The solution temperature was adjusted to 1 30" C. and 1.7 milliliters of acetylcaprolactam was mixed in to serve as an initiator. The solution was then poured into the mold heated at 1800 C. The casting was allowed to cure 10 minutes before being removed from the mold.

Example 161 ~~ A 40% calcined kaolinite clay reinforced nylon laminate was prepared by reacting a caprolactam slurry between 1100-0 aluminum sheets. The mold was prepared as described in Example 158 above. A mixture of 230.0 grams of E-caprolacta m, 1.5 grams FLECTOL H, and 2.0 grams of PEI-1000 was heated under nitrogen to 1300 C. To this stirred solution was added 120.0 grams Alsilate W calcined kaolin, keeping the slurry temperature above 1000 C. To the resultant slurry was added 1.2 milliliters of All 100 silane. The mixture was evacuated and dried by distilling 50 milliliters of caprolactam. The vacuum was released to nitrogen and the slurry cooled to 100" C.To this mixture was added 3.2 milliliters of 3 molar ethylmagnesium bromide in diethyl ether followed by thorough degassing under vacuum. The vacuum was released to nitrogen and 1 milliliter of acetylcaprolactam added to the catalyzed slurry followed by stirring for 30 seconds. The slurry was poured into the mold heated at 1800 C. and allowed to cure for 10 minutes before being removed from the mold.

Examples 162- 163 These Examples illustrate the fabrication of metal-thermoplastic-metal laminates using adhesive adhesion agents.

The laminates were prepared using 0.0127 cm (0.005 inch, 5 mils) thick 1100-0 aluminum as the metal layers. The aluminum surface was degreased by immersion in toluene followed by an acetone rinse as described in Example 1 above and then cleaned/etched by immersion in a 50.0 gram/liter aqueous solution of Apex 764 M at 70"C. for a period of 2 minutes. The aluminum was removed from the cleaning/etching solution and rinsed with hot running water while siping with a clean cloth (a Webrilb Litho Pad is convenient) followed by a hot water rinse without wiping and thereafter blown dry with a jet of clean nitrogen. The aluminum was then heated in an oven at 1100 C. for 5 minutes and 1300 C. for 10 minutes, respectively, for Example 162 and Example 163.

Example 162 ~~ A 0.00508 cm (0.002 inch, 2 mils) thick wet film of GMS 263 [poly(2-ethylhexylacrylate-comethylacrylate-co-acrylic acid-co-glycidylmethacrylate) or simply acrylate copolymer] adhesive at 25% solids was applied to the cleanedietched surface of the aluminum and allowed to air dry for 15 minutes, then at 90" C. for 2 minutes.

A poly(vinyl chloride) (PVC) sheet was wiped with an acetone-moistened clean cloth, sanded with 400-grit emery paper, wiped again with an acetone-moistened clean cloth, and dried in a nitrogen-purged vacuum oven at 60 C.

The treated aluminum layers and the PVC were assembled, with the adhesive-treated surfaces facing the PVC, and laminated under pressure of 200 C. for twenty minutes. The laminate was cooled under pressure to below 70c C. and removed from the press. The properties of the laminate are tabulated in Table 1.

Example 163 ~ An epoxy adhesive consisting of 67:33 weight mixture of EPONX 871 :UPON 828 (aliphatic epoxy resin, weight per epoxide, 390-470 and unmodified bisphenol A epoxy resin, weight per epoxide, 185-192, respectively, available commercially from Shell Chemical Company, Houston, Texas 77002) with EPON' curing agent V-25 [a polyamide, equivalent weight (amount to react with 1 mole of epoxide) of about 163] was applied to the cleaned/etched surface of the aluminum as 0.00508 cm (0.002 inch, 2 mils) thick films.

The treated aluminum layers and a sheet of nylon 6,6 were assembled, with the adhesive-treated aluminum surfaces facing the nylon 6,6 and laminated under pressure at 285 C. for 10 minutes, cooled under pressure to 200 C. and removed from the press. The properties of the laminate are tabulated in Table 1.

Example 168 The properties of the metal-thermoplastic-metal laminates prepared as described in Examples 2-163 and the component metal layers and thermoplastic core layers thereof are tabulated in Tables 1, 2 and 3 respectively. Specimens for all the tests were preconditioned at 23 C. (73 F.) for at least 18 hours. Except for the coefficient of linear thermal expansion and heat distortion temperature measurements, all tests were done at 23e C. and 50% relative humidity. All non-laminated polyamide specimens were kept dry, as-molded in sealed cans with anhydrous magnesium perchlorate or anhydrous calcium sulfate desiccants during the preconditioning period at 23 C. All other specimens were preconditioned at 50% relative humidity.

It is to be understood that the values for the thickness of the thermoplastic reported in Table 1 represent an approximate average of the values for the various laminate specimens employed in the physical tests performed on the laminate, it being understood that minor variations in thickness may exist among such specimens obtained from the experimental laminate samples prepared.

Unless otherwise indicated, the reported tensile properties for the metals are for the metal before being subjected to the thermal conditions of lamination and these values would not be expected to substantially change after being subjected to the thermal conditions of lamination in the corresponding Examples herein. TABLE 1 Properties of Metal-Thermoplastic-Metal Laminates Metal Thermoplastic Example Type Thicknessa,cm Type Thickness,cm TR 2 1100-0 Aluminum 0.0127 Polypropylene 0.157 0.162 3 " 0.0127 HDPE 0.1570.162 4 " 0.0127 " 0.165 0.154 5 5052-0 Alminum 0.0127 " 0.173 0.147 6 " 0.0762 " .178 0.0354 7 Lithoplate Aluminum 0.0140 0.277 0.101 8 1100-0 Aluminum 0.0127 HDPE/10% 0.150 0.169 FLBREGLASS 9 1145-0 Aluminium 0.0127 LDPE 0.0838 0.303 10 " 0.0127 " 0.114 0.223 11 1100-0 Aluminum 0.0127 " 0.168 0.151 12 " 0.00254 " 0.465 0.0109 13 " 0.0127 " 0.124 0.205 14 " 0.0127 " 0.0313 0.312 15 5052-0 Alumlnum 0.0127 " 0.163 0.156 16 " 0.0127 " 0.122 0.208 17 " 0.0127 " 0.0787 0.323 18 " 0.0152 " 0.102 0.298 19 Lithoplate Alumlnum 0.0140 " 0.274 0.102 20 " 0.0140 " 0.272 0.103 21 " 0.0140 " 0.254 0.110 22 6061-T6 Aluminum 0.0152 " 0.124 0.245 23 1100-0 Aluminum 0.00508 Nvlon 6,6 0.178 0.0571 24 " 0.0127 " 0.295 0.0861 25 " 0.0127 " 0.216 0.118 26 " 0.0127 " 0.180 0.141 27 " 0.0254 " 0.114 0.446 28 " 0.0254 " 0.279 0.182 TABLE 1 CONT'D Effective Flexural CLTE, HDT,D IR,c Stiffness Strength Modulus Example 10 b C ' C. % 103 N/m 106 N/m 109 N/m2 2 23.6 158 72.0 329.19 64.25 8.69 3 130 92.5 428.29 41.54 10.13 4 29.2 5 28.6 86.0 94.45 12.82 6 66.60 6.65 7 97.89 14.48 8 24.5 129 90.9 56.19 9.72 9 94.0 49.71 12.96 10 93.0 45.50 1268 11 23.8 96 92.0 295.22 33.09 6.62 12 30.2 47 33.0 7.65 1.39 13 101 91.0 39.57 7.93 14 93.9 45.78 8.48 15 23.9 100 83.0 84.80 9.86 16 81.0 106.86 11.72 17 85.0 18 86.0 19 69.63 6.41 20 75.14 8.62 21 77.21 7.93 22 247.94 166.15 10.75 23 46.3 136 11.5 137.19 5.52 24 35.8 228 19.0 127.54 11.44 25 > 250 128.23 11.44 26 29.0 > 250 27.0 1034.84 114.44 19.17 27 28 28.6 > 250 39.5 131.68 17.72 TABLE 1 CONT'D Tensile Strength, 106 N/m2 Elongation, % Modulus Gls IZOD, Notchedd Example Yield Fail Yield Fail 109 N/m2 N-m N-m/m 2 3 28.27 24.82 14.3 35.0 4 5 48.26 47.57 17.0 26.0 6 37.23 36.54 16.0 22.0 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 91.00 82.04 17.7 25.5 2.79 28 TABLE 1 CONT'D Metal Thermoplastic Example Type Thicknessa,cm Type Thicknesa,cm TR 29 1100-Aluminum 0.0254 Nylon 6,6 0.173 0.294 30 " 0.0254 " 0.0240 0.540 31 5052-0 Aluminum 0.00254 " 0.180 0.0282 32 " 0.00762 " 0.178 0.0856 33 " 0.00702 " 0.173 0.0561 34 " 0.0127 " 0.165 0.154 35 " 0.0127 " 0.160 0.159 36 " 0.00762 " 0.133 0.115 37 " 0.00254 " 0.284 0.179 38 " 0.00762 0.232 0.0540 39 " 0.0127 " 0.175 0.145 40 " 0.0127 " 0.175 0.145 41 " 0.0127 " 0.168 0.151 42 " 0.0127 " 0.168 0.151 43 " 0.0127 " 0.127 0.200 44 " 0.0127 " 0.0711 0.357 45 " 0.0127 " 0.0483 0.526 46 304 Stainless 0.00254 " 0.182 0.0279 Steel-annealed 47 " 0.000254 " 0.531 0.000957 48 " 0.00254 " 1.112 0.00457 49 " 0.00127 " 0.528 0.00481 50 " 0.00127 " 0.290 0.00876 51 " 0.00127 " 0.279 0.00910 52 " 0.00254 " 0.493 0.0103 53 " 0.00127 " 0.174 0.0146 54 " 0.00254 " 0.292 0.0174 55 " 0.00506 " 0.173 0.0587 TABLE 1 CONT'D Effective Flexural CLTE, HDT,b IR,c Stiffness Strength Modulus Example 10 b C. 1 C. % 103 N/m 10 N/m 109N/m2 29 26.8 > 250 68.0 126.16 26.96 30 25.0 > 246 92.5 120.64 21.51 31 45.6 168 17.0 231.66 129.61 5.86 32 34.9 > 246 49.0 159.94 12.34 33 157.18 10.27 34 30.6 > 250 809.66 177.18 13.89 35 27.5 72.0 746.63 179.93 18.89 36 30.2 > 246 53.5 273.51 183.38 13.44 37 55.8 166 11.0 133.05 5.45 38 34.6 > 250 30.0 144.77 9.65 39 832.25 173.73 16.61 40 908.24 175.80 18.13 41 774.82 178.55 17.37 42 780.95 183.38 17.51 43 26.3 > 246 79.0 358.60 201.30 16.34 44 25.6 87.0 161.44 202.68 28.95 45 24.7 8.0 191.655 40.33 46 33.1 > 250 33.0 511.64 174.42 12.68 47 134 3659.59 117.89 3.34 48 178 41148.50 131.68 4.76 49 178 50 150 51 153 52 49.0 > 250 19.0 5743.28 143.40 7.51 53 > 250 54 38.9 > 250 24.0 1346.17 147.53 8.27 55 26.8 59.0 690.07 210.96 18.20 TABLE 1 CONT'D Tensile Strength,10b N/m2 Elongation,% Modulus Gls IZOD, Notchedd Example Yield Fail Yield Fail 109 N/m2 N-m N-m/m 29 30 31 32 101.34 93.76 19.0 27.0 33 97.89 95.83 13.0 15.2 34 113.06 106.86 17.0 21.5 35 110.30 103.41 17.0 22.0 36 37 38 39 103.41 97.89 17.0 23.5 40 108.93 99.96 18.0 23.5 41 108.93 102.72 17.0 23.0 42 108.24 103.24 14.5 19.0 43 44 45 46 47 48 49 50 51 52 53 54 55 TABLE 1 CONT'D Metal Thermoplastic Example Type Thickness@, cm Type Thickness,cm TR 304 Stainless 56 Steel-annealed 0.00762 Nylon 6,6 0.163 0.0935 57 " 0.00762 " 0.107 0.142 58 " 0.00762 " 0.0533 0.286 59 6061-T6 Aluminum 0.0152 " 0.122 0.249 60 " 0.0152 " 0.109 0.279 61 " 0.0152 " 0.180 0.169 62 " 0.0152 " 0.251 0.121 63 6061-0 Aluminum 0.0152 " 0.160 0.190 64 " 0.0152 " 0.112 0.271 65 " 0.0152 " 0.168 0.181 66 Lithoplate Aluminum 0.0140 " 0.259 0.108 67 " 0.0140 " 0.161 0.174 68 " 0.0140 " 0.147 0.190 69 " 0.0140 " 0.0978 0.286 70C 1010 Low Carbon 0.00762 " 0.80 0.0847 Steel-annealed 71 " 0.00508 " 0.279 0.0354 72 " 0.00762 " 0.277 0.0550 73 " 0.00508 " 0.173 0.0587 74 " 0.00508 " 0.119 0.0854 75 " 0.00762 " 0.119 0.128 76 (304 Stainiless 0.00508) Steel-annealed ( ) 0.264 0.0768 (6061-0 Aluminum 0.0152 77 (304 Stainless Steel-annealed 0.00508 " ( ) 0.260 0.0734 (3003-H25 Aluminum 0.0140 TABLE 1 CONT'D Effective Flexural CLTE, HDT,b IR,c Stiffness Strength Modulus Example 10-6 C. 1 C. % 103 N/m 106 N/m 109 N/m2 56 22.3 70.0 751.88 222.68 21.58 57 21.6 82.0 309.05 253.01 27.51 58 17.8 85.0 131.85 297.13 65.91 59 81.0 606.72 260.59 27.64 60 307.47 29.78 61 75.0 196.48 22.61 62 33.5 191.65 17.65 63 62.0 160.63 18.27 64 137.19 30.89 65 139.95 24.68 66 164.77 15.24 67 169.59 23.65 68 162.01 25.58 69 166.15 31.44 70 16.2 > 250 66.5 211.65 21.58 71 159.94 15.58 72 175.80 18.68 73 17.8 > 250 47.0 159.94 22.54 74 493.43 156.49 36.61 75 762.21 183.38 50.40 76 (32.8e > 250f 45.0f) (158.56' 16.41f) ( ) ( ) (35.5g > 250h 43.0h) (166.15h 17.58h) 77 (23.2e > 250f 45.0f) (159.94f 16.34f) ( ) ( ) (34.7g > 250h 43.0n) (166.83h 17.17h) TABLE 1 CONT'D Tensile Strength,10 N/m2 Elongation, % Modulus GIS IZOD, Notchedd Example Yield Fail Yield Fail 109 N/m2 N-m N-m/m 56 57 58 59 60 134.43 123.40 3.24 61 110.30 104.79 2.83 62 63 64 98.58 91.69 15.5 21.0 3.10 65 100.65 92.38 13.0 18.5 3.24 66 67 68 69 70 116.51 108.24 13.0 19.0 3.79 71 72 73 104.79 104.10 16.0 18.0 3.45 74 75 76 77 TABLE 1 CONT'D Metal Thermoplastic Example Type Thicknessd,cm Type Thickness,cm TR 78 1100-0 Aluminum 0.0127 ZYTEL@ ST-801 0.173 0.147 79 " 0.0127 VYDYNE@R-240 0.165 0.154 80 6061-0 Aluminum 0.0152 " 0.160 0.190 81 6061-T6 Aluminum 0.0152 " 0.122 0.249 82 5052-0 Alumlnum 0.0127 " 0.165 0.154 83 " 0.0127 " 0.152 0.167 84 " 0.0127 VYDYNE@ R-220 0.168 0.151 85 C 10010 Low Carbon 0.00508 VYDYNE@ R-240 0.124 0.0819 Steel-annealed 86 304 Stainless 0.00762 " 0.112 0.136 Steel-annealed 87 1100-0 Aluminum 0.0127 Nylon 6,6/10% 0.160 0.159 Fiberglass 88 " 0.0127 Nylon 6 0.168 0.151 89 " 0.0127 Nylon 6/10% 0.157 0.162 Fiberglass 90 1100-0 Aluminum 0.0127 PARN 56/4 0.208 0.122 (crystalline) 91 " 0.0127 PARN 56/44 0.178 0.143 (amorphous) 92 " 0.0127 PET 0.154 0.165 93 " 0.0127 PET 0.254 0.100 94 Lithoplete Aluminum 0.0140 PET 0.279 0.100 95 1100-0 Aluminum 0.0127 PET 0.168 0.151 (amorphous) 96 " 0.00508 PET/11.7% HYTREL" 0.216 0.0470 4056 97 " 0.0127 " 0.216 0.118 TABLE 1 CONT'D CLTE, HDT,b IR,c Stiffness Strength Modulus Example 10 b C 1 C. 5 103 N/m 106 N/m 109 N/m2 78 30.2 > 250 47.0 598.32 84.11 12.41 79 24.8 239 27.0 682.54 159.25 15.93 80 26.3 239 54.0 183.38 19.72 81 82 83 28.3 240 78.0 216.47 21.79 84 34.2 240 184.07 19.58 85 18.2 > 237 66.5 317.93 211.65 21.03 86 19.3 > 240 78.0 408.86 278.52 32.19 87 26.6 238 26.0 147.53 14.27 88 24.3 218 33.0 211.71 12.82 89 25.0 217 27.0 135.81 12.41 90 40.0 207 20.0 83.42 10.07 &commat;;=1.5% 91 29.0 122 24.5 91.69 9.03 92 29.5 240 30.1 126.85 14.75 93 37.4 110.30 13.86 94 28.4 152.36 15.72 95 29.0 79 36.0 90.31 13.99 96 52.0 116 18.0 97.21 6.48 97 28.8 238 39.0 97.89 11.72 TABLE 1 CONT'D Tensile Strength, 105 N/m2 Elongstion, % Modulus GIS IZOD, Notchedd Example Yield Fail Yield Fail 109 N/m2 N-m N-m/m 78 79 9.04 80 9.04 81 9.04 82 > 18.08 83 113.75 10.0 8.27 > 18.08 84 104.10 2.7 11.10 < 0.68 85 86 87 88 89 90 91 92 93 94 1.36 37.37 95 48.04 96 97 TABLE 1 CONT'D Metal Thermoplastic Example Type Thicknessd,cm Type Thickness,cm TR 98 1100-0 Auminum 0.0127 PET/1.7% 0.65 0.154 99 " 0.0254 " 0.138 0.278 100 " 0.0508 " 0.152 0.668 101 " 0.0127 ' 0.264 0.0962 102 " 0.0127 " 0.249 0.102 103 " 0.0127 " 0.312 0.0814 104 " 0.0127 " 0.150 0.169 105 " 0.0127 " 0.165 0.154 106 50520-0 aLUMINUM 0.0127 PET/11.75 0.203 0.125 HYTREL#4056 107 " 0.00762 " 00.175 0.0871 108 " 0.0127 " 0.165 0.154 109 " 0.0127 " 0.165 0.154 110 6061-0 aLUMINUM 0.0152 " 0.160 0.190 111 " 0.0152 " 0.160 0.190 112 " 0.0152 " 0.160 0.190 113 " 0.0152 " 0.0914 0.333 114 6061-T6 Aluminum 0.0152 " PET/11.7% 0.249 0.122 HYTREL#4056 115 " 0.0152 " 0.163 0.187 116 " 0.0152 " 0.0914 0.333 117 Lithoplate Aluminum 0.0140 " 0.290 0.0966 118 C 1010 Low Carbon 0.00508 " 0.117 0.0888 Steel-annealed 119 " 0.00508 " 0.208 0.0488 120 1100-0 Aluminum 0.0127 PET/11.1% 0.282 0.0901 PETBCP TABLE 1 CONT'D Effective Flexural CLTE, HDT,b IR,c Stiffness Strength Modulus Example 10 C. 1 C. 5 10 N/m 10 N/m 109 N/m2 98 99 28.1 238 80.5 114.44 18.61 100 24.8 244 93.5 97.89 25.51 101 244 101.34 11.79 102 240 104.10 12.41 103 104.10 11.86 104 25.2 54.0 598.14 115.82 15.72 105 26.8 815.44 94.45 19.03 106 26.8 243 74.0 149.60 14.82 107 126.16 10.62 108 239 109 110 73.0 127.54 15.79 111 240 109.61 20.41 112 113 90.0 138.57 19.44 114 29.2 75.0 173.04 17.72 115 203.37 27.30 116 79.0&commat;r=3% 230.95 35.377 117 119.96 12.00 118 19.3 > 240 78.0 291.54 174.42 22.96 119 18.7 239 53.0 144.77 12.13 120 249 111.68 12.20 TABLE 1 CONT'D Tensile Strength, 106 N m2 Elongation. % Modulus GIS IZOD.Notchedu Examle Yield Fail Yield Fail 109 N,m2 N-m N-m/m 98 > 18.08 99 100 101 > 18.08 53.91 102 > 18.08 49.11 103 > 13.08 54.98 104 63.42 58.60 4.3 11.7 2.34 > 18.08 87.01 105 74.73 106 107 72.39 65.49 6.25 14.0 26.20 > 18.08 108 78.59 73.77 8.9 17.8 2.55 > 18.08 109 > 18.08 110 111 70.32 64.11 2.41 112 > 18.08 113 114 84.11 77.90 3.9 7.9 9.65 6.33 32.21 115 25.83 89.62 4.1 7.7 11.72 9.94 109.96 116 108.93 104.10 7.4 8.1 17.24 6.78 168.68 117 > 18.08 59.79 118 119 120 > 18.08 47.51 TABLE 1 CONT'D Metal Thermoplastic Example Type Thicknessd,cm Type Thickness,cm 121 6061-0 Aluminum 00.0152 PET/11.1% 0.249 0.122 PETBCP 122 0.0152 " 00.163 0.187 123 " 0.0152 " 0.85 0.184 124 " 0.0162 " 0.0914 0.333 125 6061-T6 Aluminum 0.0152 " 0.163 0.187 126 1100-0 Aluminum 0.0127 PET-b-5% 0.163 0.187 PBO-100 127 " 0.0127 PET-b-24% PBO-10000 128 " 0.0127 PET/23.5% 0.236 0.108 HYTREL"4056 129 " 0.0127 ' 0.282 0.0901 130 " 0.0127 " 0.282 0.0901 131 " 0.0127 " 0.165 0.154 132 Lithoplate Aluminum 0.0140 0.282 0.0993 133 1100-0 Aluminum 0.0127 PEt/10% PC 0.183 0.139 134 " 0.0127 PET/1 80/20 0.165 0.154 135 " 0.0127 PET/1 80/20 0.170 0.149 (amorphous) 136 " 0.0127 0.142 0.179 137 " 0.0127 PET/1 80/20 11.7% HYTREL#4056 0.282 0.0901 138 UTHOPLATE Aluminum 0.0140 " 0.282 0.0993 139 1100-0 Aluminum 0.0127 PET 0.165 0.154 140 " 0.0127 " 0.282 0.0901 141 Lithoplate Aluminum 0.0140 " 0.282 0.0993 142 1100-0 Aluminum 0.0127 PBT/11.7% HYTREL#4056 0.279 0.0910 TABLE 1 CONT'D Effective Flexural CLTE, HDT.d IR,' Stiffness Strength Modulus Example 10 b C. ' C. 5 103 N m 10 N,m 109N m2 121 28.1 52.5 126.16 15.17 122 112.20 27.16 123 246 124 109.61 31.99 125 168.21 39.50 126 27.9 243 30.0 113.06 10.27 127 228 34.47 7.86 128 27.6 238 38.5 79.28 12.75 129 103.41 13.03 130 242 84.80 9.10 131 77.21 19.17 132 30.4 239 83.42 13.72 133 23.9 219 23.0 119.96 13.72 134 28.8 177 27.0 126.47 15.24 135 27.4 80 43.0 85./49 9.51 136 74 42.0 101.34 12.68 137 81.36 12.89 138 95.83 13.99 139 25.7 > 207 36.0&commat;;r-4% 96.52 16.75 140 101.34 13.86 141 225 145.46 15.03 142 54.46 7.58 TABLE 1 CONT'D Tensile Strength, 10 Nm2 Elongation, % Modulus GIS IZOD, Notched@ Example Yield Fail Yield Fail 109 N/m2 N-m N-m/m 121 72.39 65.49 4.7 12.0 2.83 18.08 68.86 122 71.01 68.94 5.9 12.0 2.83 18.08 123 124 74.46 71.70 10.0 15.0 2.96 14.92 125 90.31 86.86 5.0 11.0 0.76 8.59 126 127 70.46 128 > 18.08 81.14 129 11.30 79.00 130 > 18.08 73.66 131 > 18.08 109.43 132 > 13.56 59.25 133 134 135 136 137 5.20 48.58 138 2.71 52.31 139 140 11.75 44.31 141 11.75 53.38 142 > 18.08 80.07 TABLE 1 CONT'D Metal Thermoplastic Example Type Thickness@,cm Type Thickness,cm TR 143 Lithoplate Aluminum 0.0140 PBT/11.7% 0.279 0.100 HYTREL 4056 144 1100-0 Aluminum 0.0127 PBT/23.5% 0.274 0.0927 HYTREL@ 4052 145 Lithoplate Aluminum 0.0140 " 0.277 0.101 146 1100-0 Aluminum 0.0127 HYTREL@ 7246 0.185 0.137 147 " 0.0127 " 0.282 0.0901 148 Lithoplate Aluminum 0.0140 " 0.282 0.0993 149 " 0.0140 HYTREL @ 6346 0.282 0.0993 150 0.0140 HYTREL @ 5555 0.264 0.106 151 @ 0.0140 HYTREL @ 4055 0.282 0.0993 152 1100-0 Aluminum 0.0127 Polycarbonate 0.122 0.208 153 " 0.0127 ABS 0.190 0.134 154 " 0.0127 PVC 0.147 0.173 155 304 Stainless 0.00254 Polysulfone 0.0864 0.0588 Steel-annealed 156 (C 1010 Low Carbon 0.00508) Steel-annealed ( ) Polysulfone 0.310 0.0654 (6061-0 Aluminum 0.0152) 157 (C 1010 Low Carbon 0.00508) Steel-annealed ( ) Polysulfone 0.311 0.0614 (3003-H25 Aluminum 0.0140 ) 158 Lithoplate Aluminum 0.0127 Nylon 6-b-20%POP 0.318 0.0799 159 1100-0 Aluminum 0.0127 " 0.318 0.0799 160 " 0.0127 " 0.318 0.0799 161 " 0.0127 Nylon 6/40% 0.318 0.0799 calcined clay TABLE 1 CONT'D Effective Flexural CLTE, HDT,@ IR,@ Stiffness Strength Modulus Example 10 @@C. @C. % 103N/m 10@N/m 109 N/m2 143 103.41 12.41 144 71.01 11.72 145 87.55 12.62 146 28.1 185 83 616.70 54.12 10.62 147 212 51.70 10.55 148 214 62.74 9.10 149 194 57.22 9.31 150 49.64 7.01 151 27.58 3.72 152 32.2 124 42.0 301.87 79.97 15.24 153 45.2 104 49.0 71.70 11.86 154 29.0 92 37.0 453.68 91.69 14.20 155 19.1 184 67.0 122.92 177.18 25.92 156 (29.3e 190f 33.0f) (149.60f 12.41f) ( ) ( ) (37.1g 155h 35.0h) (167.52h 16.75h) 157 28.4e 192f 29.0f) (159.94f 13.72f) ( ) ( ) (41.8g 123h 28.0h) (160.63h 14.75h) 158 26.6 127.54 13.79 159 25.6 72.39 5.45 160 30.4 117.20 8.00 161 27.9 130.30 11.10 TABLE 1 CONT'D Tensile Strength, 10@ Nm2 Elongation, % Modulus GIS IZOD, Notchedd Example Yield Fail Yield Fail 10@ N m N-m N-m m 143 > 18.08 104.09 144 > 18.08 77.40 145 > 18.08 112.63 146 147 > 18.08 110.50 148 > 18.08 100.89 149 > 18.08 358.71 150 16.27 768.67 151 3.16 560.49 152 153 154 155 156 157 158 159 218.86 160 161 TABLE 1 CONT'D Metal Thermoplastic Example Type Thicknessa,cm Type Thickness,cm TR 162 1100-0 Aluminum 0.0127 PVC 0.165 0.154 163 0.0127 Nylon 6,8 0.180 0.141 Effective Flexural CLTE, HDT,D 1R,C Stiffness Strength Moduius Example 106 C. 1 C. % 103 N/m 106 N/m 109 N/m2 162 40.1 86 375.24 90.17 8.76 163 39.8 234 495.01 120.92 9.17 Tensile Strength,106 N/m2 Elongation, % Modulus GIS IZOD, Notchedd Example Yield Fail Yield Fail 109 Nm2 N-m N-m/m 162 163 a Thickness for each metal layer.

b measured at 1.82 x 106 N/m2, except where noted otherwise.

c Determined, except where noted otherwise, at a strain, r, of 5% in the outer metal layers at the point of maximum deflection.

d Measured according to ASTM D 256 - 73 test method for plastics.

e Steel side.

f Steel on tension side.

g Aluminum side.

h Aluminum on tension side.

i Measured at 5.88 x 108 N/m2.

TABLE 2 Properties of Metals Metal Density@ CLTEmd IRm@ Type Thickness, cm kg/m2-cm 10 @ C. 1 % 1145-D Aluminum 0.102 27.07 23.8 95.0 " 0.0127 27.07 23.8 1100-D Aluminum 0.104 27.07 23.6 94.0 " 0.102 27.07 23.6 " 0.0508 27.07 23.6 " 0.0254 27.07 23.6 " 0.0127 27.07 23.6 3003-H14 Aluminum 0.0635 27.46 23.2 88.0 3003-H25 Aluminum 0.0140 27.46 23.2 3003-H19 Aluminum 0.0127 27.46 23.2 5052-0 Aluminum 0.0813 26.88 23.8 87.5 " 0.102 26.88 23.8 " 0.0127 26.88 23.8 " 0.00762 26.88 23.8 6061-0 aLUMINUM 0.163 27.07 23.4 91.0 " 0.0635 27.07 23.4 " 0.0152 27.07 23.4 6061-T6 Aluminum 0.0813 27.07 80.0 " 0.127 27.07 24.4 83.0 " 0.470 27.07 23.4 " 0.102 27.07 23.4 " 0.0152 27.07 23.4 304 Stainless Stell-annealed 0.122 80.26 15.5 88.0 " 0.00762 80.26 17.3 C 1008 Low Carbon Steel 0.109 92.8 C 1010 Low Carbon Steel-annealed 0.00762 78.34 15.1 TABLE 2 CONT'D Tensile Strength, 105 N/m2 FLEXURAL Modulus At Offset, % Elongation, % Modulus Stiffness Metal 105 N/m2 0.2 5.0 10.0 Fail Fail 109 N/m2 103 N/m 1145-0 Aluminum " 68.94 38.12 46.95 74.46 74.46 13.0 1100-0 Aluminum 68.94 42.74 299.26 " 68.94 39.43 256.35 " 68.94 32.04d " 68.94 79.97 30.0 " 68.94 33.85 58.25 64.87 71.01 30.1 3003-H14 Aluminum 68.94 3003-H25 Aluminum 68.94 152.36h 152.36h 152.36h 7.6h 3003-H19 Aluminum 68.94 237.84 2.3 5052-0 Aluminum 70.32 64.11 213.45 " 70.32 416.91e " 70.32 97.21 153.05 179.93 194.41 19.5 " 70.32 103.41 153.74 184.07 198.55 19.3 6061-0 Aluminum 68.94 41.23 1097.88 " 68.94 65.49 " 68.94 54.56 112.37 128.23 18.0 6061-T6 Aluminum 68.94 68.18 226.93 " 68.94 65.42 " 68.94 42.90f " 68.94 434.25f " 68.94 250.94 282.65 293.00 304 Stainless Steel-annealed 193.03 112.37 112.37 " 259.21 369.52 443.97 574.96 24.0 C 1008 Low Carbon Steel 162.01 1308.70 162.01 1308.70 C 1010 Low Carbon 326.78 349.53 372.28 375.03 23.0 Steel-annealed 199.93-206.82 TABLE 2 CONT'D Flexural Strength. 106 N/m2 At Strain, r. % Metal 0.5 1.0 3.0 5.0 Maximum 1145-0 Aluminum 67.77 77.90 99.27 106.17 106.17 " 1100-0 Aluminum 74.46 87.55 118.58 128.92 128.92 " 70.32 70.28 99.96 104.79 104.79 " " " 3003-H14 Aluminum 3003-H25 Aluminum 3003-H19 Aluminum 5052-0 Aluminum 255.77 320.57 379.17 317.81 380.55 " " " 6061-0 Aluminum 101.34 130.30 173.73 201.99 " " 6061-T6 Aluminum 324.71 488.10 548.07 537.73 554.28 " 310.23 535.66 587.37 598.40 598.40 " " " 304 Stainless Steel-annealed 441.91 556.36 703.19 754.23 779.02 " C1008 Low Carbon Steel 483.27 503.26 598.40 623.91 C 1010 Low Carbon Steel-annealed TABLE 2 CONT'D Metal Densitya CLTEma IRmb Type Thickness,cm kg/m2-cm 10-b C.-1 % Low Carbon Steel Paint Test Panel 0.0965 91.0 1977 Oidsmobile Delt 88 Hood - Aluminum 0.109 84.0 1977 Oldsmobile Delts 88 Hood -Steel 0.0864 92.7 1977 Chevrolet Monte Carlo Hood -Steel 0.0838 92.5 1977 Chevrolet Monte Carlo Hood -Steel 0.0813 78.14 a Taken from: Lynch, Handbook of materials of Science, Vol. II, CRC Press, Cleveland, 1975, except where noted otherwise.

b Determined, except where noted otherwise, at a strain, r. of 5% in the outer layers at the point of maximum deflection.

c Observed.

d Calculated from the average of 42.74 and 39.43 moduli, 41.08, for 0.104 cm and 0.102 cm thick 1100-0 aluminum, respectively.

e Calculated from 64.11 modulus for 0.102 cm thick 5052-0 aluminum.

f Calculated from the average of 68.18 and 65.42 moduli, 66.80, for 0.0813 cm and 0.127 cm thick 6061-T6 aluminum, respectively.

g Calculated from 133.05 modulus for 0.0838 cm thick steel from 1977 Chevrolet Monte Carlo Hood.

h Values are for the metal before subjection to the thermal conditions of lamination.

Values for the metal after subjection to such conditions are: Tensile strength (106 N/m2) = 111 (# 0.2% offset, 130 (# 0.5% offset, 134 (# fail.

Tensile elongation (# fail = 9.8% TABLE 2 CONT'D Tensile Strength, 106 N/m2 Flexural Modulus At Offset, % Elongation, % Modulus Stiffness Metal 106 N/m2 0.2 5.0 10.0 Fail Fail 109 N,m2 103 N/m Low Carbon Steel Paint Test Panel 173.73 1977 Oldsmobile Delts 88 Hood -Aluminum 62.67 506.04 1977 Oldemobile Delta 88 Hood - Steel 167.52 668.88 1977 Chevrolet Monte Carlo Hood 133.05 485.73 1977 Chevrolet Monte Carlo Hood - Steel 443.00g TABLE 2 CONT'D Flexural Strength, 106 N/m2 at Strain. r. % Metal 0.5 1.0 3.0 5.0 Maximum Low Carbon Steel Paint Test Panel 606.67 686.64 744.55 751.45 1977 Oldsmobile Delta 88 Hood - Aluminum 283.34 388.82 483.27 520.50 523.25 1977 Oldsmobile Delta 88 Hood - Steel 477.75 513.60 581.16 588.06 1977 Chevrolet Monte Carlo Hood - Steel 330.91 383.31 463.28 467.41 477.06 1977 Chevrolet Monte Carol Hood - Steel TABLE 3 Properties of Thermoplastics Flexural Thermoplastic Density@ CLTE HDT@@ IR@@ Modulus Stiffness Strength Type Thickness,cm kg.m2-cm 10 b C. 1 C. % 109 N m2 103 N m 106 N m2 Polypropylene 0.577 8.99d 0.28 329.19 " 0.323 8.99d 144.9 60 2.3 0.28 57.43 39.71 " 0.244 8.99d 0.28 24.86 HDPE 0.323 9.48e 188.6 46 2.89 0.28 57.43 23.03 HDPE/10% fiberglass 0.315 71.6 56 17.0 1.54 25.78 LDPE 0.323 9.16' 5.4 0.050 10.33 5.72 " 0.320 9.16' 187.7 35 0.050 Nylon 6,6 0.138 11.37e 110.2 1,3 2.62 699.52 110.99 " 0.132 77 ZYTEL# ST.801 0.130 10.79e 130.9 62 1.2 1.45 323.06 72.39 VYDYNER R-240 0.146 13.88e 87.5 109 5.6 4.96 1504.28 142.71 VYDYNER R-220 0.128 14.59E 83.5 99 Nylon 6,6/10% fiberglass 0.138 81.2 113 3.0 3.61 142.71 Nylon 6 0.135 11.29e 133.6 65 0.8 2.55 104.79 Nylon 6/10% fiberglass 0.133 68.0 100 2.4 3.93 146.84 PARN 56/44 (crystalline) 0.145 12.15f 57.6 117 0.4 3.03 119.27 " 0.080 57.6 117 1.5 4.14 95.14 PARN 65/44 ((@ R=2%) (amorphous) 0.128 11.73f 63.9 117 0.38 2.41 120.65 PET (crystalline) 0.136 13.75f 92.7 89 0.81 2.83 118.58 PET (amorphous) 0.333 13.32g 83.2 68 0.78 2.21 83.42 PET/11.7% HYTREL# 4056 0.211 112.0 TABLE 3 CONT'D Tensile Modulus Strength, 106 N/m2 Elongation, % Tm, C. Tgcg, C.

Thermoplastic 109 N/m2 Yield Fail Yield Fail Polypropylene 170 -(13-8) " 1.24 31.71 11.0 > 50.0 170 -(13-8) " 170 -(13-8) HDPE 0.69 19.92 18.5 > 50.0 140 -125 HDPE/10% fiberglass 0.76 19.65 12.0 > 50.0 140 LDPE 0.22 8.41 98.0 > 100.0 114 -125 " 114 -125 Nylon 6,6 2.96 83.42 63.42 18.0 36.0 263 50 " ZYTELR ST-801 1.79 51.64 7.1 > 50.0 265 VYDYNER R-240 5.03 95.83 92.38 3.9 12.0 246 VYDYNER R-220 6.55 85.14 1.8 241 Nylon 6,6/10% fiberglass 3.79 91.00 3.7 260 Nylon 6 2.69 75.14 4.6 > 50.0 220 40-87 Nylon 6/10% fiberglass 3.93 94.45 3.3 218 PARN 56/44 (crystalline) 78.74 2.2 301 " 301 PARN 56/44 (amorphous) 2.55 88.00 5.6 > 50.0 PET (crystalline) 3.03 77.21 4.8 257 81 PET amorphous) 2.21 54.95 3.9 50.0 67 PET/11.7% hytrelR 4056 TABLE 3 CONT'D Flexural Thermoplastic Density@ CLTE HDT,9 IR@ Modulus Stiffness Strength Type Thickness,cm kg mR-cm 10@ . C.C. . 10@Nm2 103Nm 106N m2 PET 11.7%. HYTREL 4056 0.351 82 4.6 1.86 64.11 PET 23.5 . HYTREL 4056 0.318 93.1 82 1.86 67.63 PET 11.1 . PETBCP 0.318 91.8 68 5.9 2.00 73.08 PET@b-5 . PBO- 1000 0.353 116.3 75 1.6 2.69 97.21 PET (crystalline) 10 . Poivcarbonate 0.343 83.7 88 1.2 2.65 115.13 PET I 80 20 (crystalline) 0.361 13.71 82.3 75 1.1 2.76 114.44 PET I 80 20 (amorphous) 0.366 13.40 78.5 75 4.5 2.17 91.00 PBT 0.345 13.08E 140.6 52 0.66 2.21 79.97 HYTREL 7246 0.343 12.48E 166.0 53 0.40 5.31 132.73 22.75 Polycarbonate 0.268 12.17c 72.4 121 0.0 2.55 301.87 102.72 0.180 12.17d 92.80 ABS 0.318 10.58e 108.4 81 6.7 2.07 65.15 PVC 0.279 13.90g 3.38 453.68 0.155 13.90g 3.38 79.67 0.150 13.90g 63.7 74 1.4 3.38 102.03 Polysulfone 0.378 12.38c 90.9 160 0.6 2.34 96.52 0.203 12.38c 2.34 122.92 0.175 12.38c 2.34 78.27 a Literature values, as noted.

b Measured at 1.82 x 10 N m2 except where noted otherwise.

c Determined, except where noted otherwise. at a strain. r. of 5 . in the outer iavers at the point of maximum deflection.

TABLE 3 CONT'D Tensile Modulus Strength, 106 N/m2 Elongation, % Tm%C. Tgcg, C.

Thermoplastic 109 N,m2 Yield Fail Yield Fail PET,11.7% HYTRELR 4056 2.34 58.60 5.6 > 50.0 257 PET/23.5% HYTRELR 4056 1.79 45.50 5.0 > 50.0 257 PET/11.1%PETBCP 3.09 73.42 260 PET-b-5% PBO-1000 2.83 68.94 41.23 5.0 30.0 256 PET (crystalline)/ 10% Polycarbonate 2.83 74.46 4.5 > 50.0 242 PET/I 80/20 (crystalline) 2.83 76.52 4.5 18.5 202 PET/I 80/20 (amorphous) 3.03 63.49 3.45 > 50.0 PBT 2.14 55.84 12.0 > 50.0 230 17-80 HYTREL" 7246 0.55 27.58 22.0 > 50.0 216 Polycarbonate 2.07 60.67 6.1 > 50.0 145 " 145 ABS 1.93 41.36 3.0 PVC 81 " 81 " 2.28 108.24 4.5 > 50.0 81 Polysulfone 2.55 73.77 70.32 6.0 7.3 176 " 176 " 176 TABLE 3 CONT'D Flexural Thermoplastic Densitya CLTEc HDTcb IRcc Modulus Stiffness Strength Type Thickness,cm kg/m2-cm 10 60C. 1 C. % 109 N/m2 103 N/m 106 N/m2 d Value for commercial product. Taken from: International Plastics Selector, Cordura Publications, Inc., La Jolla, CA, 1977.

e Taken from product brochure for commercial product.

f Experimental value.

g Taken from: Bandrup and Immergut, Eds., Polymer Handbook, 2nd ed., John Wiley & Sons, New York, 1975.

Thus, it is apparent that there has been provided, in accordance with the present invention, metal-thermoplastic-metal laminates and a process for preparing same that fully satisfies the objects and advantages set forth hereinabove. While the invention has been described with respect to various specific examples and embodiments thereof, it is understood that the invention is not limited thereto and that many alternatives, modifications and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, it is intended to embrace all such alternatives, modifications, and variations as fall within the spirit and broad scope of the invention.

Claims

1. A metal-thermoplastic-metal laminate having in combination: an inelastic ratio less than about 93%; a coefficient of linearthermal expansion less than about63 > c 10-6 C.-'; a flexural stiffness of at least about 52.53 > c x 103 N/m; and a maximum weight of no more than about 9.76 kg/m2; said laminate comprising: a thermoplastic core layer; and a metal layer laminated on each side of the thermoplastic core layer, each metal layer having a minimum thickness of about 0.00127cm; provided that aluminum is not the metal layer on both sides of the laminate when the thermoplastic core layer is high density polyethylene and further provided that when polypropylene is the thermoplastic core and aluminum is the metal layer laminated on each side of the core, the laminate has a maximum weight of about 5.37 kg/m2; wherein the thickness ratio of the sum of the metal layer-thicknesses to the thermoplastic core layer thickness is described by the region of numerical overlap of the parameter TR(YSm/TSC) as determined from the areas defined by the relationships of TR(YSm/TSC) to IR, and CLTE,,the lower boundary of said areas being defined by the equation of a straight line y = mx + b in which y is they-axis parameters of IR, and CLTE" is the x-axis parameter of TR(YSm/TSC), m is the slope of the straight line, and b is the intercept on they-axis, with the proviso that:: when y is IR,, m is 108 and b is zero (0) for values of x from zero (0) to 0.65, and m is zero (0) and b is 70 for values ofxgreater than 0.65; and when y is CLTE1, m is -3.6:: 10-4 and b is 45 x 10-6 for values of from zero (0) to 0.1, and mis zero (0) and b is 9 x 10~6forvalues of x greaterthan 0.1; and the upper boundary of said areas being defined by the equation of a straight line as defined hereinabove, with the proviso that: when y is IR,, m is 280 and b is 30 for values of x from zero (0) to 0.25, and m is zero (0) and b is 100 for values of x greater than 0.25; and when y is CLTE" m is -2.88:: 10-3 and b is 216 x 10-6 for values of from zero (0) to 0.05, m is -1.29 x 10-4 and b is 78.5 x 10-6 for values of x from 0.05 to 0.26, and m is zero (0) and b is 45 x 10-6 for values of x greater than 0.26; wherein: IR, is the inelastic ratio of the laminate as measured in flexure at 5% strain in the outer metal layers at the point of maximum deflection; CLTE, is the coefficient of linear thermal expansion of the laminate; TR is the thickness ratio of the sum of the metal layer-thicknesses to the thermoplastic core layer thickness; YSm is the.thickness-weig ht-average tensile yield strength of the two metal layers at an offset of 5% elongation; and TSC is the tensile strength of the thermoplastic core layer.

2. The laminate of Claim 1 wherein the thermoplastic core layer is an olefin-based thermoplastic.

3. The laminate of Claim 2 wherein the olefin-based thermoplastic is polypropylene.

4. The laminate of Claim 2 wherein the olefin-based thermoplastic is high-density polyethylene.

5. The laminate of Claim 2 wherein the olefin-based thermoplastic is low-density polyethylene.

6. The laminate of Claim 3 wherein the metal layers-are not aluminum.

7. The laminate of Claim 4 wherein the metal layers are not aluminum.

8. The laminate of Claim 5 wherein the metal layers are not aluminum.

9. The laminate of Claim 3 wherein only one of the metal layers is aluminum.

10. The laminate of Claim 4 wherein only one of the metal layers is aluminum.

11. The laminate of Claim 5 wherein only one of the metal layers is aluminum.

12. The laminate of Claim 2 wherein the olefin-based thermoplastic is a multi-polymer derived from monomers selected from the group consisting of ethylene, propylene, 1-butene, 3-methylbutene and 4-methylpentene.

13. The laminate of Claim 1 wherein the thermoplastic core layer is an amide-based thermoplastic.

14. The laminate of Claim 13 wherein the amide-based thermoplastic is nylon 6,6.

15. The laminate of Claim 13 wherein the amide-based thermoplastic is nylon 6.

16. The laminate of Claim 13 wherein the amide-based thermoplastic is nylon 6-co-6,6.

17. The laminate of Claim 13 wherein the amide-based thermoplastic is a partially aromatic nylon.

18. The laminate of Claim 17 wherein the partially aromatic nylon is a nylon 6, terephthalic acid-co-6, isophthalic acid.

19. The laminate of Claim 18 wherein the nylon 6, terephthalic acid-co-6, isophthalic acid is nylon 0-70% 6, terephthalic acid-co-100-30% 6, isophthalic acid.

20. The laminate of Claim 1 wherein the thermoplastic core layer is an ester-based thermoplastic.

21. The laminate of Claim 20 wherein the ester-based thermoplastic is a poly(alkylene terephthalate).

22. The laminate of Claim 21 wherein the poly(alkylene terephthalate) has an alkylene group containing from 2 to 10 carbon atoms.

23. The laminate of Claim 22 wherein the poly(alkylene terephthalate) is poly(ethylene terephthalate).

24. The laminate of Claim 22 wherein the poly(alkylene terephthalate) is poly(butylene terephthalate).

25. The laminate of Claim 22 wherein the poly(alkylene terephthalate) is a block copolymer-modified poly(alkylene terephthalate).

26. The laminate of Claim 25 wherein the block copolymer modified poly(alkylene terephthalate) is a poly(ethylene terephthalate)lpoly(butylene tere-co-isophthalate)-block-poly(butylene glycol) blend.

27. The laminate of Claim 1 wherein the thermoplastic core layer is an arylene carbonate-based thermoplastic.

28. The laminate of Claim 27 wherein the arylene carbonate-based thermoplastic is polycarbonate.

29. The laminate of Claim 1 wherein the thermoplastic core layer is a styrenic-based thermoplastic.

30. The laminate of Claim 29 wherein the styrenic-based thermoplastic is an ABS resin.

31. The laminate of Claim 1 wherein the thermoplastic core layer is a vinyl-based thermoplastic.

32. The laminate of Claim 31 wherein the vinyl-based thermoplastic is poly(vinyl chloride).

33. The laminate of Claim 1 wherein the thermoplastic core layer is an arylene sulfone-based thermoplastic.

34. The laminate of Claim 33 wherein the arylene sulfone-based thermoplastic is polysulfone.

35. The laminate ofClaims 1,2,3,4,5,6,7,8,9,10, 11,12,13,14,15,16,17, 18, 19,20,21,22,23,24,25, 26, 27, 28, 29. 30, 31, 32, 33 or 34 wherein the thermoplastic core layer material contains an added modifying agent.

36. The laminate of Claim 35 wherein the added modifying agent is high modulus, high performance fibers.

37. The laminate of Claim 36 wherein the high modulus, high performance fibers are glass fibers.

38. The laminate of Claim 37 wherein the glass fibers are present in concentrations of between about 1% and about 33% by weight.

39. The laminate of Claim 35 wherein the added modifying agent is a mineral filler.

40. The laminate of Claim 39 wherein the mineral filler is present in concentrations of between about 1% and about 50 0 by weight.

41. The laminate of Claim 40 wherein the mineral filler is calcined kaolinite clay.

42. The laminate of Claim 41 wherein the calcined kaolinite clay is present in a concentration of about 20% to about 45% by weight.

43. The laminate of Claim 1 wherein the thermoplastic core layer is partly crystalline.

44. The laminate of Claim 43 wherein the partly crystalline thermoplastic core layer has a degree of crystallinity of at least 15%.

45. The laminate of Claim 44 wherein each of the metal layers has a melting point greater than the crystalline melting point of the partly crystallinethermoplastic core layer and the thickness ratio of the sum of the metal layer-thicknesses to the thermoplastic core layer thickness is further described by the parameter TR(YSm TSr) as determined from the area defined by the relationship of the TR(YSmtTSc) to (HDT, HDT,) (T > , - HDTc), the lower boundary of said area being defined by the equation of a straight line y = mx + b in which y is they-axis parameter of (HDT, - HDTC)!(Tm - HDTC), xis the x-axis parameter of TR(YSm/TSC), m is the slope of the straight line, and b is the intercept on they-axis, with the proviso that: m is 1 and b is zero (0) for values of x from zero (0) to 0.05, m is 10 and b is -0.45 for values of x from 0.05 to 0.12, and m is zero (0) and b is 0.75 for values of x greater than 0.12; and the upper boundary of said area being defined by the equation of a straight line as defined hereinabove, with the proviso that: m is 112.5 and b is zero (0) for values of x from zero (0) to 0.004, m is 15.3 and b is 0.389 for values of x from 0.004 to 0.04, and m is zero (0) and b is 1 for values of x greater than 0.04 wherein:: (HDT, - HDTC)!(Tm - HDTC) is a normalized heat distortion temperature variable wherein HDT, is the heat distortion temperature of the laminate; HDTC is the heat distortion temperature of the thermoplastic core layer; Tm is the crystalline melting point of the thermoplastic core layer; TR is the thickness ratio of the sum of the metal layer-thicknesses to the thermoplastic core layer thickness; YSm is the thickness-weight-average tensile yield strength of the two metal layers at an offset of 5% elongation; and TSC is the tensile strength of the thermoplastic core layer.

46. The laminate of Claim 1 wherein the metal layers laminated on each side of the thermoplastic core layer have the same composition.

47. The laminate of Claim 46 wherein the metal layers are aluminum.

48. The laminate of Claim 46 wherein the metal layers are low carbon steel.

49. The laminate of Claim 46 wherein the metal layers are stainless steel.

50. The laminate of Claim 1 wherein the metal layers have different compositions.

51. The laminate of Claim 50 wherein certain important characteristics of the metal are substantially balanced such that: (a) CLTEj = CLTEjj; (b) tjEj = tijEjj; and (c) tys = tijysjj; wherein CLTEi and CLTE1i, ti and tij, Ei and Ejj, and ys and ysjj are, respectively, the coefficients of linear thermal expansion, thicknesses, elastic moduli, and tensile yield strengths of the respective metal layers arbitrarily labeled as "i" and 'ii".

52. The laminate of Claim 51 wherein the metal layer laminated on one side of the thermoplastic core layer is aluminum and that laminated on the other side is low carbon steel.

53. The laminate of Claim 51 wherein the metal layer laminated on one side of the thermoplastic core layer is aluminum and that laminated on the other side is stainless steel.

54. The laminate of Claim 1 wherein the metal layers laminated on each side of the thermoplastic core layer are of equal thickness.

55. The laminate of Claim 1 wherein the metal layers laminated on each side of the thermoplastic core layer are of different thicknesses.

56. The laminate of Claim 1 wherein both the metal layers and the thermoplastic core layer are ductile.

57. The laminate of Claim 56 which is ductile.

58. The laminate of Claim 57 which is formable at elevated temperatures into permanently shaped structures.

59. The laminate of Claim 1 which is a substantiallyflatstructure.

60. The laminate of Claim 1 which is a shaped structure.

61. The laminate of Claim 1 wherein the thermoplastic core layer and the metal layers are uniformly laminated together via an adhesion agent interposed between the facing surfaces thereof.

62. The laminate of Claim 61 wherein the adhesion agent is an organosilane adhesion promoter.

63. The laminate of Claim 62 wherein the organosilane adhesion promoter is an amino-functional alkyltrialkoxysilane.

64. The laminate of Claim 63 wherein the amino-functional alkyltrialkoxysilane is gammaaminopropyltriethoxysilane.

65. The laminate of Claim 63 wherein the amino-functional alkyltrialkoxysilane is N-beta-(aminoethyl)gamma-aminopropyltrimethoxysilane.

66. The laminate of Claim 62 wherein the organo-silane adhesion promoter is a glycidoxy-functional alkyltrialkoxysilane.

67. The laminate of Claim 66 wherein the glycidoxy-functional alkyltrialkoxysilane is gammaglycidoxypropyltrimethoxysilane.

68. The laminate of Claim 62 wherein the organosilane adhesion promoter is a methacryloxy-functional alkyltrialkoxysilane.

69. The laminate of Claim 68 wherein the methacryloxy-functional alkyltrialkoxysilane is gammamethacryloxypropyltrimethoxysilane.

70. The laminate of Claim 62 wherein the organosilane adhesion promoter is a mixture of an amino-functional alkyltrialkoxysilane and a methacryloxy-functional alkyltrialkoxysilane.

71. The laminate of Claim 70 wherein the amino-functional alkyltrialkoxysilane and the methacryloxyfunctional alkyltrialkoxysilane of the mixture are gamma-aminopropyltriethoxysilane and gammamethacryloxypropyltrimethoxysilane, respectively.

72. The laminate of Claim 61 wherein the adhesion agent is an adhesive.

73. The laminate of Claim 72 wherein the adhesive is an epoxy resin.

74. The laminate of Claim 1 suitable for use as an automobile body panel wherein: (a) the coefficient of linear thermal expansion is less than about 45 x 106 C. 1; (b) the inelastic ratio is less than about 75%; (c) the flexural stiffness is at least about 262.65 x 103N/m; and (d) the maximum weight is less than about 6.34 kg/m2; said laminate further having a heat distortion temperature of at least about 135 C.

75. A process for the preparation of a metal-thermoplastic-metal laminate having in combination: an inelastic ratio less than about 93%; a coefficient of linear thermal expansion less than about 63 x 10-6 6 C.~l; a flexural stiffness of at least about 52.53 x 103 N/m; and a maximum weight of no more than about 9.76 kg/m2; which process comprises: disposing a metal layer having a minimum thickness of about 0.00127 cm on each side of a thermoplastic core layer, provided that aluminum is not the metal layer on both sides of the laminate when the thermoplastic core layer is high density polyethylene and further provided that when polypropylene is the thermoplastic core and aluminum is the metal layer laminated on each side of the core, the laminate has a maximum weight of about 5.37 kg/m2;; wherein the thickness ratio of the sum of the metal layer-thicknesses to the thermoplastic core layer thickness is described by the region of numerical overlap of the parameter TR(YSm/TSc) as determined from the areas defined by the relationship of the TR(YSm/TSc) to IR, and CLTE,, the lower boundary of said areas being defined by the equation of a straight line y = mx + b in which y is they-axis parameters of IR, and CLTE" is the x-axis parameter of TR(YSmiTSC), m is the slope of the straight line, and b is the intercept of they-axis, with the proviso that: when y is IR,. m is 108 and b is zerd (0) for values of x from zero (0) to 0.65, and m is zero (0) and b is 70 for values of x greater than 0.65; and whenyisCLTE" mis -3.6 x and b is45 x x 10 10-6 for values of x from zero (0) to 0.1, and mis zero (0) and b is 9 x 10-@ for values of x greater than 0.1; and the upper boundary of said areas being defined by the equation of a straight line as defined hereinabove, with the proviso that: when y is IR,, m is 280 and b is 30 for values ofx from zero (0) to 0.25, and m is zero (0) and b is 100 for values of x greater than 0.25; and when y is CLTE,, m is -2.88 x 1O- and b is 216 x 1 o-6 for values of x from zero (0) to 0.05, m is -1.29 x 10-4 and b is 78.5 x 10-b for values of x from 0.05 to 0.26, and m is zero (0) and b is 45 x 10-6 for values ofx greater than 0.26; wherein: IR, is the inelastic ratio of the laminate as measured in flexure at 5% strain in the outer metal layers at the point of maximum deflection; CLTE, is the coefficient of linear thermal expansion of the laminate; TR is the thickness ratio of the sum of the metal layer-thicknesses to the thermoplastic core layer thickness; YSm is the thickness-weight-average tensile yield strength of the two metal layers at an offset of 5% elongation; and TSc is the tensile strength of the thermoplastic core layer laminating the thermoplastic core layer and the metal layers by subjecting the combination to elevated temperatures and a pressure sufficient to maintain face-adhering contact; and cooling to ambient temperatures.

76. The process of Claim 75 wherein the thermoplastic core layer is partly crystalline, each metal layer has a melting point greater than the crystalline melting point of the thermoplastic core layer, and the thickness ratio of the sum of the metal layer-thicknesses to the thermoplastic core layer thickness is further described by the parameter TR(YSm/TSC) as determined from the area defined by the relationship of TR(YSm TSc) to (HDT, - HDTc) (Tm - HDT,), the lower boundary of said area being defined by the equation of a straight line y = mx + b in which vis they-axis parameter of (HDT, - HDT)i(Tm - HDTc), xis the x-axis parameter of TR(YSm/TSC), m is the slope of the straight line, and b is the intercept on they-axis, with the proviso that: m is 1 and b is zero (0) for values of x from zero (0) to 0.05, m is 10 and b is -0.45 for values of x from 0.05 to 0.12, and m is zero (0) and b is 0.75 for values ofx greater than 0.12; and the upper boundary of said area being defined by the equation of a straight line as defined hereinabove, with the proviso that: m is 112.5 and b is zero (0) for values of x from zero (0) to 0.004, m is 15.3 and b is 0.389 for values of x from 0.004 to 0.04, and m is zero (0) and b is 1 for values of x greater than 0.04; wherein: (HDT, - HDTc)(Tm - HDT/) is a normalized heat distortion temperature variable wherein HDT, is the heat distortion temperature of the laminate; HDTc is the heat distortion temperature of the thermoplastic core layer; Tm is the crystalline melting point of the thermoplastic core layer; TR is the thickness ratio of the sum of the metal layer-thicknesses to the thermoplastic core layer thickness; YSm is the thickness-weight-average tensile yield strength of the two metal layers at an offset of 5% elongation; and TSC is the tensile strength of the thermoplastic core layer.

77. The process of Claim 75 wherein the elevated temperatures are between about 100 C. and 350cm.

78. The process of Claim 75 wherein an adhesion agent is interposed between the facing surface of the metal layers and the thermoplastic core layer.

79. The process of Claim 75 wherein the adhesion agent is an organosilane adhesion promoter.

80. The process of Claim 79 wherein the organosilane adhesion promoter is an amino-functional alkyltrialkoxysilane.

81. The process of Claim 80 wherein the amino-functional alkyltrialkoxysilane is gammaaminopropyltriethoxysilane.

82. The process of Claim 80 wherein the amino-functional alkyltrialkoxysilane is N-beta-(aminoethyl)gamma-aminopropyltrimethoxysilane.

83. The process of Claim 79 wherein the organosilane adhesion promoter is a glycidoxy-functional alkyltrialkoxysilane.

84. The process of Claim 83 wherein the glycidoxy-functional alkyltrialkoxysilane is gammaglycidoxypropyltrimethoxysilane.

85. The process of Claim 79 wherein the organosilane adhesion promoter is a methacryloxy-functional alkyltrialkoxysilane.

86. The process of Claim 85 wherein the methacryloxy-functional alkyltrialkoxysilane is gammamethacryloxypropyltrimethoxysilane.

87. The process of Claim 86 wherein the thermoplastic core layer is polypropylene, the surfaces of which having been treated with dicumyl peroxide; the metal layers are 1100-0 aluminum; and the elevated temperature is about 2004C.

88. The process of Claim 79 wherein the organosilane adhesion promoter is a mixture of an amino-functional alkyltrialkoxysilane and a methacryloxy-functional alkyltrialkoxysilane.

89. The process of Claim 88 wherein the amino-functional alkyltrialkoxysilane and the methacryloxyfunctional alkyltrialkoxysilane of the mixture are gamma-aminopropyltriethoxysilane and gammamethacryloxypropyltrimethoxysilane, respectively.

90. The process of Claim 78 wherein the adhesion agent is an adhesive.

91. The process of Claim 90 wherein the adhesive is an epoxy resin.

92. The process of Claim 75 which further comprises: (a) applying a weather resistant protective coating to at least one of the metal surfaces of the metal-thermoplastic-metal laminate; (b) curing the protective coating at elevated temperatures; and thereafter (c) cooling to ambient temperatures.

93. A process for the preparation of a metal-thermoplastic-metal laminate which comprises: (a) orienting two metal layers to provide a spatial separation therebetween; and (b) casting a thermoplastic core layer between the two metal layers by in situ polymerization therebetween of monomeric material at polymerization conditions.

94. The process of Claim 93 wherein the monomeric material is E-caprolactam and the thermoplastic core layer is nylon 6.

95. The process of Claim 93 wherein the monomeric material is E-caprolactam, an acyl-bis-caprolactam, and polyoxypropylene glycol and the thermoplastic core layer is a nylon 6/polyoxypropylene block copolymer.

96. The process of Claim 95 wherein the acyl-bis-caprolactam is isophthaloyl-bis-caprolactam.

97. The process of Claim 93 wherein the monomeric material is e-caprolactam admixed with calcined kaolinite clay and the thermoplastic core layer is a calcined clay reinforced nylon 6.

98. The process of Claim 97 wherein the calcined kaolinite clay reinforced nylon 6 is 20% to 45% calcined kaolinite clay reinforced nylon 6.