POLYARYLETHER KETONE COMPOSITIONS AND METHOD OF COATING A METAL SURFACE

Abstract

A polyaryl ether ether composition(C) and methods of uses thereof are herein disclosed. The composition comprises a polymer blend [blend (B)] consisting of: a first polyaryl ether ketone (PAEK-1)and a second polyaryl ether ketone (PAEK-2), wherein the (PAEK-1) is crystalline and exhibits a melting temperature T.sub.m of 330 C. or higher and the (PAEK-2) is either amorphous or crystalline and exhibits a melting temperature T.sub.m of 315 C. or lower and wherein the (PAEK-1) constitutes more than 0% wt of blend (B). Composition (C) can be used in particular for the manufacture of coated metal surfaces, in particular for the coating of wires or of (part of) electronic devices.

Claims

1. A method of coating a metal surface, said method comprising applying to a metal surface a polymer composition comprising a polymer blend [blend (B)] consisting of: a first polyaryl ether ketone (PAEK-1) and a second polyaryl ether ketone (PAEK-2), wherein the (PAEK-1) is crystalline and exhibits a melting temperature Tm of 330 C. or higher and the (PAEK-2) is either amorphous or crystalline and exhibits a melting temperature T.sub.m of 315 C. or lower and wherein the (PAEK-1) constitutes more than 50% wt of blend (B) and wherein the composition is heated to a temperature higher than the melting temperature of (PAEK-1) before being applied to the metal surface.

2. The method according to claim 1 wherein the (PAEK-1) comprises recurring units (R1), wherein at least 50% moles of said recurring units comply with at least one of the formulae (J-A)-(J-Q) here below: ##STR00013## ##STR00014## wherein: each of R, equal to or different from each other, is selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; j is zero or is an integer from 1 to 4 and Y is an alkylidene group.

3. The method according to claim 2 wherein at least 50% moles of recurring units (R1) are units of formula (J-A), (J-B), (J-C) or (J-O).

4. The method according to claim 2 or 3, wherein the phenylene moieties in recurring units (R1) have 1,4- linkages.

5. The method according to any one of claims 2 to 4 wherein j is at each occurrence zero.

6. The method according to claim 5 comprising at least 98% moles of recurring units complying with formula (J-A) here below: ##STR00015##

7. The method according to any one of claims 1 to 4 wherein the (PAEK-2) comprises at least 50% moles of recurring units (R2) complying with at least one of formulae (J-A)-(J-Q) as defined in claim 2, wherein in units (J-A), (J-B) and (J-Q) the phenylene moieties have independently 1,3- and 1,4- linkages, while in units (J-C)-(J-P) the phenylene moieties have 1,4-linkages.

8. The method according to claim 7 wherein j is at each occurrence zero.

9. The method according to claim 1 in which blend (B) is a blend (B-1) comprising: a (PAEK-1) which is a polyether ether ketone comprising at least 98% moles of recurring units of formula (S-A): ##STR00016## a (PAEK-2) wherein at least 50% moles of the recurring units are a combination of units of formula (J-B) and (J-B), a combination of units of formula (J-A) and (J-D), units of formula (J-A), units of formula (J-P), or a combination of units of formulas (J-A) and (J-A), said units complying with the formulas here below: ##STR00017##

10. The method according to claim 9 in which blend (B-1) is selected from: 1) a blend (B-1a), comprising: a (PAEK-1) wherein all recurring units are units of formula (J-A) and a (PAEK-2) wherein all recurring units are a combination of units of formulas (J-B) and (J-B); 2) a blend (B-1b), comprising: a (PAEK-1) wherein all recurring units are units of formula (J-A) and a (PAEK-2) wherein all recurring units are a combination of units (J-A) and (J-D) 3) a blend (B-1c), comprising: a (PAEK-1) wherein all recurring units are units of formula (J-A) and a (PAEK-2) wherein all the recurring units are recurring units of formula (J-P); 4) a blend (B-1d), comprising: a (PAEK-1) wherein all recurring units are units of formula (J-A) and a (PAEK-2) in which at least 50% moles of the recurring units are recurring units (J-A); 5) a blend (B-1e), comprising: a (PAEK-1) which is a PEEK wherein at least 98% moles of the recurring units are units of formula (J-A) and a (PAEK-2) which is a PAEK in which at least 95% moles of the recurring units are recurring units (J-A) and (J-A)

11. The method according to any one of claims 1 to 10 wherein the polymer composition comprises a reinforcing filler.

12. The method according to claim 1 in which blend (B) is a blend (B-2) comprising a (PAEK-2) which is a PAEK wherein at least 50% moles of recurring units comply with formula (J-A) or (J-Q) here below: ##STR00018##

13. The method according to claim 11 in which blend (B-2) comprises a (PAEK-1) in which at least 50% moles of the recurring units comply with formula (J-A),with a combination of units (J-B) and (J-B) or with formula (J-C) here below: ##STR00019##

14. The method according to claim 13 in which blend (B-2) is selected from: 1) a blend (B-2a), comprising: a (PAEK-1) which is a PEEK wherein at least 98% moles of the recurring units are units of formula (J-A) and a (PAEK-2) which is a PAEK in which at least 95% moles of the recurring units are recurring units (J-A); 2) a blend (B-2b), comprising: a (PAEK-1) which is a PEEK wherein at least 98% moles of the recurring units are units of formula (J-A) and a (PAEK-2) which is a PAEK in which at least 95% moles of the recurring units are recurring units (J-Q).

15. A polymer composition comprising a polymer blend [blend (B-1)] selected from a blend (B-1a), a blend (B-1c), a blend (B-1d) and a blend (B-1e), as defined in claim 10 or a blend (B-2) as defined in claim 12.

16. A polymer composition comprising a polymer blend (B-2a) and (B-2b) as defined in claim 14.

17. A metal surface coated with a polymer composition comprising a polymer blend [blend (B)] consisting of: a first polyaryl ether ketone (PAEK-1) and a second polyaryl ether ketone (PAEK-2), wherein the (PAEK-1) is crystalline and exhibits a melting temperature T.sub.m of 330 C. or higher and the (PAEK-2) is either amorphous or crystalline and exhibits a melting temperature T.sub.m of 315 C. or lower and wherein the (PAEK-1) constitutes more than 50% wt of blend (B).

18. The metal surface of claim 17 which is the surface of a wire, or the surface of a structural part of an electronic device.

19. A wire or an electronic device or a part thereof comprising at least one surface according to claim 17 or 18.

Description

SYNTHESIS EXAMPLES

Example 1

Synthesis of Poly(Ether Bisphenol A Ketone) [Repeat Unit (J-P)]

[0186] In a 1L 4-neck reaction flask fitted with a stirrer, a N.sub.2 inlet tube, a Claisen adapter with a thermocouple plunging in the reaction medium, and a Dean-Stark trap with a condenser and a dry ice trap were introduced 169.70 g of N,N-dimethylacetamide, 254.5 g of toluene, 111.93 g of bisphenol A (0.490 mol), 84.70 g of dry potassium carbonate (0.613 mol). The flask content was evacuated under vacuum and then filled with high purity nitrogen (containing less than 10 ppm O.sub.2). The operation was repeated twice. The reaction mixture was then placed under a constant nitrogen purge (60 mL/min).

[0187] The reaction mixture was heated slowly to 130 C. An azeotrope toluene/water was collected and the water separated. The reaction mixture was held for 4 hours at 130 C. while removing water through the azeotrope. At 130 C., a solution of 107.63 g of 4,4-difluorodibenzophenone (0.493 mol) in 169.70 g of N,N-dimethylacetamide was added via an addition funnel to the reaction mixture over 30 minutes. At the end of the addition, the reaction mixture was heated to 165 C. After 40 minutes at 165 C., 4.279 g of 4,4-difluorodibenzophenone were added to the reaction mixture while keeping a nitrogen purge on the reactor. After 15 minutes, 20.78 g of lithium chloride were added to the reaction mixture. 10 minutes later, another 3.2095 g of 4,4-difluorodibenzophenone were added to the reactor and the reaction mixture was kept at temperature for 30 minutes. The reactor content was then coagulated in 2.0 L methanol. The solid was filtered off and washed with a mixture acetone/methanol (50/50) then with water at pH between 1 and 12. The last wash water had a pH between 6 and 7. The powder was then dried at 120 C. under vacuum for 12 hours yielding 171.3 g of a white powder. Analysis by SEC showed the polymer had Mn=34046, Mw=123149. By DSC, the polymer was shown to be amorphous with a Tg (half height) of 157 C. The glass transition temperature Tg and the melting temperature Tm were determined according to ASTM D3418, and as per the specific details described above, from the 2nd heat scan in a differential scanning calorimeter using a heating rate of 20 C./minute from 30 to 400 C.

[0188] Size exclusion chromatography (SEC) was performed using methylene chloride as a mobile phase. Two, 5 micron (m) mixed D SEC columns with guard columns (Agilent Technologies) was used for separation. An ultraviolet detector of 254nm was used to obtain the chromatograms. A flow rate of 1.5 mL/min and injection volume of 20 micro liters (L) of a 0.2% weight by volume (w/v) solution in mobile phase was selected. Calibration was performed using narrow calibration standards of Polystyrene (Agilent Technologies) (Calibration Curve: 1) Type: Relative, Narrow calibration standard calibration 2) Fit : 3rd order regression). Empower Pro GPC software (Waters) was used to acquire data, calibrate and determine molecular weight.

[0189] The Td 5% Loss of the polymer was 498 C. The Td 5% Loss refers to the average temperature at which the material lost 5% of its weight as determined by thermogravimetric analysis (TGA) according to the ASTM D3850 standard. TGA was performed on a TA Instruments TGA Q500 from 30 C. to 800 C. under nitrogen (60 mL/min) at 10 C./minute.

Example 2

Synthesis of Sulfonated PEEK [Repeat Units (J-A) and (J-A)]

[0190] This Example demonstrates the synthesis of the H+ and Na+ forms for sulfonated PEEK.

[0191] To demonstrate the synthesis of the H+ form of sulfonated PEEK, in a 3L 4-neck reaction flask fitted with a stirrer, a n.sub.2 inlet tube, a Claisen adapter with a thermocouple plunging in the reaction medium, and a Dean-Stark trap with a condenser and a dry ice trap were introduced 2.0 L of concentrated H.sub.2SO.sub.4 (96%) and 300.00 g of KT820FP powder (commercially available form Solvay Specialty Polymers USA, LLC). At the end of the addition, the reaction mixture was heated to 50 C. under agitation and under a nitrogen atmosphere. The mixture was held at 50 c for 6 h then coagulated under high shear (Waring blender) in 24L demineralized water. The solid was filtered off and washed with water and aq. Na.sub.2CO.sub.3 solution until pH higher than 7. The solid was then dried at 100 C. under vacuum for 12 hours yielding 578 g of a soft hygroscopic beige solid. The analysis by FTIR was shown to be identical with sulfonated PEEK, as described in Xigao et al., Brit. Polymer Journal, 1985, V17, P 4-10, which is incorporated herein by reference.

[0192] By DSC, the polymer was shown to be amorphous with a Tg (half height) of 108 C. The Td 5% Loss of the polymer was 452 C. Elemental analysis for sulfur showed that the polymer was 51% sulfonated. The synthesized copolymer was represented by the following formula:

##STR00007##

Example 3

Preparation of PEEK-PEDEK Copolymer 70/30 [Repeat Units (J-A) and (J-D)]

[0193] In a 500 mL 4-neck reaction flask fitted with a stirrer, a N.sub.2 inlet tube, a Claisen adapter with a thermocouple plunging in the reaction medium, and a Dean-Stark trap with a condenser and a dry ice trap were introduced 129.80 g of diphenyl sulfone, 18.942 g of hydroquinone, 13.686 g of 4,4-biphenol and 54.368 g of 4,4-difluorobenzophenone. The flask content was evacuated under vacuum and then filled with high purity nitrogen (containing less than 10 ppm O.sub.2). The reaction mixture was then placed under a constant nitrogen purge (60 mL/min).

[0194] The reaction mixture was heated slowly to 150 C. At 150 C., a mixture of 26.876 g of Na.sub.2CO.sub.3 and 0.1524 g of K.sub.2CO.sub.3 was added via a powder dispenser to the reaction mixture over 30 minutes. At the end of the addition, the reaction mixture was heated to 320 C. at 1 C./minute. After 10 minutes at 320 C., 6.415 g of 4,4-difluorobenzophenone were added to the reaction mixture while keeping a nitrogen purge on the reactor. After 5 minutes, 0.418 g of lithium chloride were added to the reaction mixture. 10 minutes later, another 2.138 g of 4,4-difluorobenzophenone were added to the reactor and the reaction mixture was kept at temperature for 15 minutes.

[0195] The reactor content was then poured from the reactor into a SS pan and cooled. The solid was broken up and ground in an attrition mill through a 2 mm screen. Diphenyl sulfone and salts were extracted from the mixture with acetone and water at pH between 1 and 12. The powder was then removed from the reactor and dried at 120 C. under vacuum for 12 hours yielding 73 g of a white powder. The repeat unit of the polymer is:

##STR00008##

[0196] The melt viscosity measured by capillary rheolology at 400 C., 1000 s1 using a tungsten carbide die of 0.53.175 mm was 0.19 kN-s/m.sup.2. The Td 5% Loss of the polymer was 561 C.

Example 4

Preparation of PEEK-PEDEK Copolymer 75/25 [Repeat Units (J-A) and (J-D)]

[0197] In a 500 mL 4-neck reaction flask fitted with a stirrer, a N.sub.2 inlet tube, a Claisen adapter with a thermocouple plunging in the reaction medium, and a Dean-Stark trap with a condenser and a dry ice trap were introduced 128.21 g of diphenyl sulfone, 20.295 g of hydroquinone, 11.405 g of 4,4-biphenol and 54.368 g of 4,4-difluorobenzophenone. The flask content was evacuated under vacuum and then filled with high purity nitrogen (containing less than 10 ppm O.sub.2). The reaction mixture was then placed under a constant nitrogen purge (60 mL/min).

[0198] The reaction mixture was heated slowly to 150 C. At 150 C., a mixture of 26.876 g of Na.sub.2CO.sub.3 and 0.169 g of K.sub.2CO.sub.3 was added via a powder dispenser to the reaction mixture over 30 minutes. At the end of the addition, the reaction mixture was heated to 320 C. at 1 C./minute. After 10 minutes at 320 C., 6.415 g of 4,4-difluorobenzophenone were added to the reaction mixture while keeping a nitrogen purge on the reactor. After 5 minutes, 0.418 g of lithium chloride were added to the reaction mixture. 10 minutes later, another 2.138 g of 4,4-difluorobenzophenone were added to the reactor and the reaction mixture was kept at temperature for 15 minutes.

[0199] The reactor content was then poured from the reactor into a SS pan and cooled. The solid was broken up and ground in an attrition mill through a 2 mm screen. Diphenyl sulfone and salts were extracted from the mixture with acetone and water at pH between 1 and 12. The powder was then removed from the reactor and dried at 120 C. under vacuum for 12 hours yielding 74 g of a white powder.

[0200] The repeat unit of the polymer is:

##STR00009##

[0201] The melt viscosity measured by capillary rheolology at 400 C., 1000 s1 using a tungsten carbide die of 0.53.175 mm was 0.15 kN-s/m.sup.2. The Td 5% Loss of the polymer was 557 C.

Example 5

Preparation of PEEK-PEDEK Copolymer 80/20 [Repeat Units (J-A) and (J-D)]

[0202] In a 500 mL 4-neck reaction flask fitted with a stirrer, a N.sub.2 inlet tube, a Claisen adapter with a thermocouple plunging in the reaction medium, and a Dean-Stark trap with a condenser and a dry ice trap were introduced 127.7 g of diphenyl sulfone, 21.861 g of hydroquinone, 9.207 g of 4,4-biphenol and 54.835 g of 4,4-difluorobenzophenone. The flask content was evacuated under vacuum and then filled with high purity nitrogen (containing less than 10 ppm O.sub.2). The reaction mixture was then placed under a constant nitrogen purge (60 mL/min).

[0203] The reaction mixture was heated slowly to 150 C. At 150 C., a mixture of 27.339 g of Na.sub.2CO.sub.3 and 0.171 g of K.sub.2CO.sub.3 was added via a powder dispenser to the reaction mixture over 30 minutes. At the end of the addition, the reaction mixture was heated to 320 C. at 1 C./minute. After 4 minutes at 320 C., 6.577 g of 4,4-difluorobenzophenone were added to the reaction mixture while keeping a nitrogen purge on the reactor. After 5 minutes, 1.285 g of lithium chloride were added to the reaction mixture. 10 minutes later, another 2.192 g of 4,4-difluorobenzophenone were added to the reactor and the reaction mixture was kept at temperature for 15 minutes.

[0204] The reactor content was then poured from the reactor into a SS pan and cooled. The solid was broken up and ground in an attrition mill through a 2 mm screen. Diphenyl sulfone and salts were extracted from the mixture with acetone and water at pH between 1 and 12. The powder was then removed from the reactor and dried at 120 C. under vacuum for 12 hours yielding 72 g of a white powder.

[0205] The repeat unit of the polymer is:

##STR00010##

[0206] The melt viscosity measured by capillary rheolology at 400 C., 1000 s1 using a tungsten carbide die of 0.53.175 mm was 0.20 kN-s/m.sup.2. The Td 5% Loss of the polymer was 561 C.

Example 6

Preparation of a PEmEK Polymer [Repeat Units (J-A)]

[0207] In a 500 mL 4-neck reaction flask fitted with a stirrer, a n.sub.2 inlet tube, a Claisen adapter with a thermocouple plunging in the reaction medium, and a Dean-Stark trap with a condenser and a dry ice trap, were introduced 128.63 g of diphenyl sulfone, 28.853 g of resorcinol and 58.655 g of 4,4-difluorobenzophenone. The flask content was evacuated under vacuum and then filled with high purity nitrogen (containing less than 10 ppm O.sub.2). The reaction mixture was then placed under a constant nitrogen purge (60 mL/min).

[0208] The reaction mixture was heated slowly to 150 C. At 150 C., a mixture of 28.742 g of Na.sub.2CO.sub.3 and 0.182 g of K.sub.2CO.sub.3 was added via a powder dispenser to the reaction mixture over 30 minutes. At the end of the addition, the reaction mixture was heated to 275 C. at 1 C./minute. After 1 minute at 275 C., 6.860 g of 4,4-difluorobenzophenone were added to the reaction mixture while keeping a nitrogen purge on the reactor. After 5 minutes, 0.447 g of lithium chloride were added to the reaction mixture. 10 minutes later, another 2.287 g of 4,4-difluorobenzophenone were added to the reactor and the reaction mixture was kept at temperature for 15 minutes.

[0209] The reactor content was then poured from the reactor into a stainless steeel pan and cooled. The solid was broken up and ground in an attrition mill through a 2 mm screen. Diphenyl sulfone and salts were extracted from the mixture with acetone and water at pH between 1 and 12. The powder was then removed from the reactor and dried at 120 C. under vacuum for 12 hours yielding 67 g of a light brown powder. The repeat unit of the polymer is 100% (J-A):

##STR00011##

[0210] The melt viscosity measured by capillary rheology at 410 C., 46 s1 according to ASTM 3835 was 0.33 kN-s/m2.

[0211] By DSC, the polymer was found to be amorphous with a Tg of 122 C.

Example 7

Preparation of a PEDEKmK Polymer [Repeat Units (J-Q)]

[0212] In a 500 mL 4-neck reaction flask fitted with a stirrer, a n.sub.2 inlet tube, a Claisen adapter with a thermocouple plunging in the reaction medium, and a Dean-Stark trap with a condenser and a dry-ice trap, were introduced 128.44 g of diphenyl sulfone, 29.980 g of 4,4-biphenol and 53.188 g of 1,3-bis(4-fluorobenzoyl)benzene. The flask content was evacuated under vacuum and then filled with high purity nitrogen (containing less than 10 ppm O2). The reaction mixture was then placed under a constant nitrogen purge (60 mL/min).

[0213] The reaction mixture was heated slowly to 150 C. At 150 C., a mixture of 17.662 g of Na.sub.2CO.sub.3 and 0.111 g of K.sub.2CO.sub.3 was added via a powder dispenser to the reaction mixture over 30 minutes. At the end of the addition, the reaction mixture was heated to 320 C. at 1 C./minute. After 1 minute at 275 C., 2.076 g of 1,3-bis(4-fluorobenzoyl)benzene were added to the reaction mixture while keeping a nitrogen purge on the reactor. After 5 minutes, 0.550 g of lithium chloride were added to the reaction mixture. 10 minutes later, another 1.038 g of 1,3-bis(4-fluorobenzoyl)benzene were added to the reactor and the reaction mixture was kept at temperature for 15 minutes.

[0214] The reactor content was then poured from the reactor into a stainless steel pan and cooled. The solid was broken up and ground in an attrition mill through a 2 mm screen. Diphenyl sulfone and salts were extracted from the mixture with acetone and water at pH between 1 and 12. The powder was then removed from the reactor and dried at 120 C. under vacuum for 12 hours yielding 69 g of a white powder. The repeat unit of the polymer is 100% (J-Q):

##STR00012##

[0215] The melt viscosity measured by capillary rheology at 410 C., 46 s.sup.1 according to ASTM 3835 was 0.23 kN-s/m2.

[0216] By DSC, was polymer was found to exhibit a T.sub.m of 306 C.

Preparation of Polymer Blends and Tests

General Description of the Compounding Process for the Manufacture of Neat Polymer Blends

[0217] Neat polymer blends consisting of a PEEK as PAEK-1 and a PEAK-2 in Table 1 were produced by melt compounding on a Coperion ZSK 26 or a Berstorff co-rotating intermeshing twin-screw extruder. Compounding conditions on each machine utilized barrel temperature set points between 340 and 350 C.

[0218] Testing specimens were molded using a temperature profile of 349-354 C. rear, 371-377 C. middle, and 377-390 C. front zones with mold temperatures between 150 and 200 C. for blends of PEEK/PAEK-2.

Results and Discussion

[0219] Neat (i.e. without additional ingredients) blends of PEEK and PEEK-PEDEK [blends (B-1b) in the description] having the composition indicated in Table 1a show advantageous performance over neat PEEK (Table 1). Blends of PEEK/PEEK-PEDEK demonstrate high flow, shown by examples E5 and E6, similar to Ketaspire KT-890 PEEK (comparative example C1). The PEEK/PEEK-PEDEK modulus and strength are similar to those of neat PEEK (comparative example C1) while exhibiting higher ductility by tensile strain at break in comparison to neat PEEK. Additionally, notched impact and dynatup impact performance demonstrated similar or better performance over neat PEEK. The improved performance in Dynatup failure mode, where the number of brittle versus ductile failure modes are noted, is especially improved in example E5 where only 25% PAEK-2 blended into PEEK improves the performance of the blend to 100% ductile failure mode in dynatup testing. Similar performance was observed in compositions (C) comprising blends of PEEK/PEEK-PEDEK and glass fibers as reinforcing fibers with results shown in Table 2. The results show that the use of PEEK-PEDEK as PAEK-2 improves flow, modulus, and strength of over control compositions comprising only PEEK-PEDEK and glass fibers (controls C12-C14). Also, the data shows improved ductility by tensile strain at break for examples E8 through E11 in comparison to a control composition comprising PEEK and glass fibers (comparative example C7) and notched impact over such control composition. The notched Izod performance was improved while tensile strength and tensile modulus exhibited similar performance to PEEK, comparative example C7.

TABLE-US-00001 TABLE 1 Neat PEEK/PAEK-2 blends - Components C1 E1 E2 E3 E4 E5 E6 Component(s) Ketaspire KT-890 NL 100 75 60 75 60 75 60 PEEK PEEK-PEDEK copolymer 25 40 70/30 (synthesis example 3) PEEK-PEDEK copolymer 25 40 75/25 (synthesis example 4) PEEK-PEDEK copolymer 25 40 80/20 (synthesis example 5) Test MV, Pa * s, 400 C., 1000/s 77 89 99 DSC, Tg, 2nd pass, C. 145 149 150 150 150 147 149 DSC, .Math. Hm 2nd Heat, J/g 68.52 61.13 54.46 59.46 54.99 64.42 58.55 Tensile Modulus, ksi, ASTM 573 553 528 551 529 549 533 D638 Tensile Strain @ Break, %, 13 18 22 18 20 19 21 ASTM D638 Tensile Strength @ Yield, 15,300 14,800 14,100 14,800 14,500 14,800 14,500 psi, ASTM D638 Notched Izod, ft-lb/in, ASTM 0.97 1.03 1.25 1.13 1.07 1.00 0.94 D256 [0.01] [0.28] [0.03] [0.11] [0.06] [0.06] [0.02] Dynatup, Total Energy, ft-lbf, 42.6 35.6 52.2 34.4 57.6 57.2 61.1 ASTM D3763 [16.5] [21.4] [15.4] [22.0] [1.1] [2.0] [2.3] % Ductile Breaks 40 40 80 40 100 100 100 Note: values in brackets are measurement standard deviations

TABLE-US-00002 TABLE 2 Compositions comprising PEEK/PAEK blends and glass fibers - Composition and Properties C7 E8 E9 E10 E11 C12 C13 C14 Components Ketaspire KT- 70 42 52.5 42 42 890 NL PEEK PEEK-PEDEK 28 70 copolymer 70/30 (synthesis example 3) PEEK-PEDEK 17.5 28 70 copolymer 75/25 (synthesis example 4) PEEK-PEDEK 28 70 copolymer 80/20 (synthesis example 5) Owens Corning 30 30 30 30 30 30 30 30 OCV 910A glass fiber PEEK/PAEK-2 100/0 60/40 75/25 60/40 60/40 0/100 0/100 0/100 ratio Test MV, Pa * s, 400 C., 183 277 228 248 252 423 341 408 1000/s Tensile Modulus, 1,750 1,590 1,650 1,650 1,540 1,390 1,410 1,400 ksi, ASTM D638 Tensile Strain @ 2.6 3.0 2.9 3.0 3.3 3.7 3.8 3.9 Break, %, ASTM D638 Tensile Strength, 28,100 25,200 25,900 27,000 24,400 21,100 21,600 21,000 psi, ASTM D638 Notched Izod, ft- 1.43 1.86 1.59 1.60 1.59 3.30 3.03 3.30 lb/in, ASTM D256 [0.03] [0.06] [0.03] [0.10] [0.08] [0.02] [0.07] [0.09] Note: Values in brackets are measurement standard deviations.

Examples C15 and E16

Improved Adhesion on Chemically Nano-Etched Metal Substrates

[0220] The following examples illustrate the improved adhesion obtained from overmolding compositions of the invention onto a chemically nano-etched metal surface as described in European patent applications EP 1459882 A1 and EP1559542 A1 assigned to Taiseiplas corporation (so-called nano-molding technology or NMT-treated) when compared to compositions of state of the art.

Blending and Compounding

[0221] For Example E16 in Table 3, the two polymeric ingredients of the composition (PAEK-1, PAEK-2) were first tumble blended for 20 minutes in a 5-gallon drum to create a premix of the resins. The premix was next metered to the feed throat of a 25 mm Berstorff co-rotating intermeshing twin-screw extruder having 8 barrel sections. The resin mix was metered at a rate of 17.5 lb/hr using a gravimetric feeder. Fiberglass was fed at barrel section 6, also using a gravimetric feeder, at a rate of 7.5 lb/hr for a total compounding throughput rate of 25 lb/hr. The Barrel section temperature settings during compounding were 330 C. for barrel zone 2 and 340 C. for barrel zones 3-8 and for the adaptor and die. The temperature of the melt was monitored during the compounding run using a handheld temperature probe and was determined to be in the 380-390 C. range. Vacuum venting was provided at barrel section 7 achieving a vacuum level of 25 in Hg to remove moisture and any other volatile residues from the compound. The extrudate of the compounded was stranded from the die and cooled in a water bath and then cut into cylindrical pellets approximately 3.0 mm in length and 2.7 mm in diameter. The composition of comparative example C15 was prepared in a similar manner to that described above for example E 16.

Injection Molding

[0222] The pellets obtained from the compounding process above were first dried in a 150 C. desiccated convection air oven for approximately 16 hours (overnight) in preparation for injection molding. Injection molding was performed for two purposes: 1) to produce 3.2 mm (0.125 in) thick ASTM tensile and flexural specimens for mechanical property testing. Type I tensile ASTM specimens and 5 in0.5 in0.125 in flexural specimens were injection molded using 30% glass fiber reinforced PEEK injection molding guidelines provided by the supplier (Solvay Specialty Polymers). 2) Injection molding of lap shear over-molded specimens was also carried out on NMT-treated aluminum grade A-6061 coupons that are 4.5 mm long1.75 mm wide2 mm thick. These coupons were prepared and supplied by Taiseiplas Corp. A small rectangular specimen of polymer was over-molded onto the aluminum coupons using a three-plate mold manufactured and supplied by Taiseiplas Corp. The rectangular strip of plastic over-molded onto the aluminum coupons was 4.5 cm in length, 1 cm in width and 3 mm in thickness as nominal dimensions. The plastic piece was over-molded onto the aluminum coupons such that there was an overlap area between the two pieces defined by nominal dimensions of 10 mm5 mm to provide a nominal overlap area of 50 mm.sup.2. The molding temperatures used for injection molding the overmolded lap shear assemblies were as follows: barrel temperature settings on the 150 ton Toshiba injection molder were: 360/365/371/371 C. for the rear/mid/front/nozzle zones, respectively. The mold temperature was set at 200 C. with actual mold temperature achieved being around 195 C.

Lap Shear Adhesion Testing

[0223] The over-molded aluminum/plastic assembly that was obtained from the molding described above was tested for lap shear strength in an Instron tensile test apparatus following the guidelines of ASTM D1002. A positioning fixture supplied by Taiseiplas was used to hold the assembly in place in the Instron grips and to maintain the alignment of the metal and plastic pieces during the tensile pull on the two materials to assure that the force applied on the lap interface is a purely shear force. A pull rate of 0.05 in/min was used for this testing and the lap shear strength of each specimen was calculated by dividing the load needed to break apart each assembly divided by the nominal overlap area of the joint. The lap shear strength is what we refer to here interchangeably as adhesion strength of the plastic to the metal substrate.

[0224] Results and Discussion

[0225] As can be seen from the data tabulated in Table 3, the lap shear adhesion strength of the composition of Example E16, comprising 52% wt PEEK and 17.5% wt PEKK [blend (B-1a) in the description] outperformed the the control composition containing PEKK only by a large margin (comparative example C15). In fact the adhesion of the composition prepared according to the instant invention is approximately double that of the state of the control composition. In addition to achieving this greatly improved adhesion toward the treated aluminum, the mechanical properties of the composition according to this invention are for the most part on par with those of the control composition.

TABLE-US-00003 TABLE 3 Lap shear adhesion of glass fiber reinforced PEEK and PEEK/PEKK blend compositions onto NMT treated A-6061 aluminum coupons Example C15 E16 Ketaspire KT-880P PEEK 70.0 52.5 Cypek DS-E PEKK 17.5 OCV-910A Glass Fiber 30.0 30.0 PEEK/PEKK ratio 100/0 75/25 NMT Lap Shear Mean (MPa) 17.1 34.7 NMT Lap Shear Std. Deviation (MPa) 7.8 4.3 Tensile Strength (psi) 24900 27100 Tensile Modulus (Ksi) 1580 1640 Tensile Elongation at Break (%) 3.1 2.7 Flex Strength (psi) 40800 40200 Flex Modulus (Ksi) 1660 1650 Flex Strain at Break (%) 3.0 2.8 Notched Izod (ft-lb/in) 1.6 1.5 Unnotched Izod (ft-lb/in) 17.8 15.3 Melt Visc. at 1000 1/s and 400 C. (kPa-s) 0.35 0.26

Examples C17 to E24

Preparation of Glass Fiber-Reinforced Compositions

[0226] For Examples E19 to E24 in Table 4, the two polymeric ingredients of the composition (PAEK-1 and PAEK-2) were first tumble blended for 20 minutes in a 5-gallon drum to create a premix of the resins. The premix was next metered to the feed throat of a 25 mm Berstorff co-rotating intermeshing twin-screw extruder having 8 barrel sections. The resin mix was metered at a rate of 12.6 lb/hr using a gravimetric feeder. Fiberglass was fed at barrel section 6, also using a gravimetric feeder, at a rate of 5.4 lb/hr for a total compounding throughput rate of 18 lb/hr. The Barrel section temperature settings during compounding were 330 C. for barrel zone 2 and 340 C. for barrel zones 3-8 and for the adaptor and die. The temperature of the melt was monitored during the compounding run using a handheld temperature probe and was determined to be in the 380-390 C. range. Vacuum venting was provided at barrel section 7 achieving a vacuum level of 25 in Hg to remove moisture and any other volatile residues from the compound. The extrudate of the compounded was stranded from the die and cooled in a water bath and then cut into cylindrical pellets approximately 3.0 mm in length and 2.7 mm in diameter. The composition of Control C15 was prepared in a similar manner to that described above for Examples E19 to E24. The control compositions C17 and C18 were prepared in a similar manner as for C15, except that the temperature setting for the Barrel section temperature settings during compounding were 300 C. for barrel zone 2 and 340 C. for barrel zones 3-8 and for the adaptor and die.

[0227] The melting temperature T.sub.m was determined as the peak temperature of the melting endotherm on the 2nd heat scan in DSC at 20 C./minute.

TABLE-US-00004 TABLE 4 PAEK-2 Polymer Source Repeat (synthesis PAEK- PEEK PAEK- GF PEEK/PAEK-2 Composition Unit example) 2 T.sub.m wt % 2 wt % wt % wt/wt ratio C15 None 70.0 0 30.0 100/0 C17 (J-A) and Ex. 3. 296 0 70.0 30.0 0/100 (J-D) C18 (J-A) and Ex. 5 312 0 70.0 30.0 0/100 (J-D) E19 (J-P) Ex. 1 ND.sup.a 52.5 17.5 30.0 75/25 E20 (J-A) and Ex. 2 ND.sup.a 65.8 4.2 30.0 94/6 (J-A) E21 (J-A) and Ex. 3 296 52.5 17.5 30.0 75/25 (J-D) E22 (J-A) and Ex. 4 304 52.5 17.5 30.0 75/25 (J-D) E23 (J-A) and Ex. 5 312 52.5 17.5 30.0 75/25 (J-D) E24 (J-B) and Cypek ND.sup.a 52.5 17.5 30.0 75/25 (J-B) DS-E PEKK .sup.aamorphous polymers: no melting endotherm detected on the second heat DSC scan .sup.bthe composition of E19 comprises a blend (B-1C), that of E20 a blend (B-1d) those of E21-E23 comprise a blend (B-1b) and that of E24 a blend (B-1a)

Examples C25 to E33

Adhesion of Compositions C15, C17 and C18 and E19 to E14 to Aluminum

[0228] These Examples demonstrate the adhesion of PEEK/PAEK-2 overmold compositions to aluminum A-6061 substrates using poly(aryl ether) adhesive compositions. To demonstrate adhesion, lap shear samples were formed and the lap shear stress was measured at room temperature and according to the ASTM D1002 standard with a grip distance of 3.5 inches. Lap shear samples were formed by overmolding the metal substrates with the described PEEK/PAEK-2 compositions. The metal substrates were formed from aluminum 6061 alloy and had a double butt lap joint with a surface area of about 0.25 square inches (In).

[0229] The aluminum substrates were laser etched (Minilase, from Tykma Technologies) to form a crosshatch pattern having a distance of about 100 m between parallel lines. Following etching, the metal substrates were rinsed in acetone or isopropanol and dried in a vacuum oven at about 50 Torr to about 100 Torr and at about 50 C. or 100 C.

[0230] A PEEK/PAEK-2 composition was deposited on the metal substrates using injection molding (pellets predried at 120 C./25 Hg vacuum for 4 hours). In particular, the metal substrates were preheated to a temperature of about 190 C. to about 200 C. in an oven and, subsequently, on a hotplate. The preheated substrates were then placed in an injection mold heated to about 199 C. The PEEK/PAEK-2 composition was then injected, into the mold, at a temperature between from about 370 C. to about 380 C. to form the lap shear samples. The lap shear sample was removed from the mold and allowed to continue to cool to room temperature.

[0231] The lap shear stress values, measured at 0.05 in/minute, listed in TABLE 5 are averaged over the number of lap shear samples in the corresponding Sample Set. The enthalpy of fusion, indicative of the degree of crystallinity of the compositions, derived from the melting endotherm on the 2nd heat scan in DSC at 20 C./minute is also indicated in table 5. The values are expressed relative to the polymer content of the composition, i.e. excluding the filler content. This is obtained by dividing the values measured on the filled compositions by the polymer content (=0.70).

[0232] The results of the lap shear test measurements are reported with respect to lap shear stress at break as well and were further analyzed to determine the type of failure at break. In particular, following failure of the lap shear samples, the samples were analyzed to determine if the failure was Adhesive, Cohesive, Partially Cohesive or Specimen Break. Adhesive failures were characterized by a lack of visually detectable polymer on the metal and lack of visually detectable metal on the polymer, on the fracture surface of the sample. Cohesive failures were characterized by a visually detectable amount of polymer on the metal or a visually detectable amount of metal on the polymer, on the fracture surface of the sample. Partially Cohesive failures were analogous to Cohesive failures but showed a reduced amount of polymer on the metal or metal on the polymer. Specimen Break was characterized by fracture in the bulk polymer and not at the metal/polymer interface.

TABLE-US-00005 TABLE 5 lap shear test on aluminum Heat of Lap PEEK/ fusion (J/g shear Std. No. PAEK-2 polymer) of Stress dev. Cohesive Example composition composition (psi) (psi) Failures Failure Type C25 C15 53.7 409 120 0/5 adhesive C26 C17 30.0 1614 165 5/5 3 partially cohesive + 2 specimen breaks C27 C18 42.7 1079 324 2/5 1 partially cohesive + 1 specimen break + 3 adhesive E28 E19 45.4 799 243 0/5 adhesive E29 E20 54.2 635 261 0/5 adhesive E30 E21 47.7 1316 180 5/5 4 partially cohesive + 1 specimen break E31 E22 49.0 1157 306 3/5 3 partially cohesive + 2 adhesive E32 E23 50.6 964 175 3/5 3 partially cohesive + 2 adhesive E33 E24 49.1 1081 253 5/5 4 partially cohesive + 1 specimen break

[0233] Referring to TABLE 5, the results demonstrate that for the lap shear samples tested, the compositions according to the invention significantly improve the adhesion to aluminum as compared to PEEK (C15), while retaining a good level of crystallinity (>42.8 J/g heat of fusion). The improvement observed with only 25 wt % of PAEK-2 [PAEK-2 to (PAEK-1+PAEK-2) ratio] as in E21 and E23 is surprising based on the lap shear results of C17 and C18, comprising only PAEK-2 and glass fibers [100 wt % PAEK-2 to (PAEK-1+PAEK-2) ratio]. Therefore, these results demonstrate that in the compositions according to the invention there is a unique combination of adhesion and crystallinity (chemical resistance).

Examples C34 to E36

Adhesion of Compositions to Copper

[0234] Three of these compositions were evaluated also for adhesion to copper. The conditions of testing were the same as for examples C25 to E33 except that the metal substrates were formed from copper (electrical grade)

[0235] The copper substrates were rinsed with acetone, air dried then chemically etched by immersion in an aqueous solution containing 12.2 wt % ferric sulfate pentahydrate and 7.8% sulfuric acid (for 1 minute at 65 C.), rinsing with demineralized water, immersion in an aqueous solution containing 5.5 wt % potassium bichromate and 9.9 wt % sulfuric acid (5 minutes at room temperature) and rinsing with demineralized water. Following etching, the metal substrates were rinsed with demineralized water and dried in a vacuum oven at about 50 Torr to about 100 Torr and at about 120 C.

TABLE-US-00006 TABLE 6 PEEK/ Heat of fusion Lapshear Std. No. PAEK-2 (J/g polymer) Stress dev. Cohesive Failure Example composition of composition (psi) (psi) Failures Type C34 C15 53.7 255 90 0/5 adhesive E35 E19 45.4 402 251 0/5 adhesive E36 E20 54.3 393 177 0/5 adhesive

[0236] Referring to TABLE 6, the results demonstrate that for the lap shear samples tested, the compositions according to the invention significantly improve the adhesion to copper as compared to a comparative composition containing PEEK only (C34), while retaining a good level of crystallinity (>42.8 J/g heat of fusion).

Examples E37 -E38

Preparation of Glass Fiber-Reinforced Compositions

[0237] For the preparation of the compositions of Examples E37, E38 and C39 in Table 7, the ingredients of the compositions were first tumble blended for 20 minutes in a 5-gallon drum to create a premix of the resins. A 40% glass filled PEEK was produced from Ketaspire 880KT PEEK as a precursor to the final compositions. A Coperion ZSK 26 co-rotating intermeshing extruder was used to produce the precursor compound. Upstream barrel temperatures were at a set point of 360 C., a transition barrel at 350 C., downstream barrels at 340 C., and the adapter and die at a set point of 350 C. before the melt exited the extruder to be cooled and pelletized. OCV 910A glass fibers were introduced into the polymer melt downstream in the extruder. The measured melt temperature of the extrudate exiting the die was 390 C., acquired by hand-held temperature probe. The final composition was achieved by mixing the 40% glass filled PEEK pellets thus obtained and additional PEEK (KetaSpire KT-880P) (for the preparation of C39) or polymers powder PAEK-2 prepared according to synthesis examples 6 and 7 (for the preparation on E37 and E38) to reach a final level of 30 wt % glass fibers in the composition. The premix was next metered to the feed throat of a 18 mm Leistritz co-rotating intermeshing twin-screw extruder having 8 barrel sections. The resin mix was metered at a rate of 5 to 6 lb/hr using a gravimetric feeder. For the preparation of C39, the Barrel section temperature settings during compounding were 370 C. for barrel zone 1 and 355 C. for barrel zones 2-5 and for the adaptor and die. The temperature of the melt was monitored during the compounding run using a handheld temperature probe and was determined to be in the 380-390 C. range. Vacuum venting was provided at barrel section 7 achieving a vacuum level of 8 mm Hg to remove moisture and any other volatile residues from the compound. The extrudate of the compounded was stranded from the die and cooled in a water bath and then cut into cylindrical pellets approximately 3.0 mm in length and 2.7 mm in diameter. The compositions E37 and E38 were prepared in a similar manner as for C39, except that the temperature setting for the Barrel section temperature settings during compounding were 280 C. for barrel zone 1 and 345 C. for barrel zones 2-5 and for the adaptor and die.

[0238] The melting temperature T.sub.m was determined as the peak temperature of the melting endotherm on the 2nd heat scan in DSC at 20 C./minute.

TABLE-US-00007 TABLE 7 PEAK-2 Polymer Source PEEK/PAEK- Repeat (synthesis PAEK-2 PEEK PAEK-2 GF 2 wt/wt Composition Unit example) T.sub.m ( C.) wt % wt % wt % ratio E37 (J-A) Ex. 6 ND.sup.a 52.5 17.5 30 75/25 E38 (J-Q) Ex. 7 306 52.5 17.5 30 75/25 C39 None 70 0 30 100/0 .sup.ano melting endotherm detected on the second heat DSC scan

C40 and E41-E42

Adhesion of Compositions C39, E37 and E38 to Aluminum

[0239] Adhesion of compositions E37,E38 and C39 to aluminum was evaluated in the same way as in examples C25 to E33; the results of these tests are reported in Table 8 below.

[0240] The enthalpy (heat) of fusion, indicative of the degree of crystallinity of the compositions, derived from the melting endotherm on the 2nd heat scan in DSC at 20 C./minute is also indicated in Table 8.

[0241] Also in these tests, following failure of the lap shear samples, the samples were analyzed to determine if the failure was Adhesive, Cohesive, Partially Cohesive or Specimen Break; the meaning of these expressions is the same as explained above.

TABLE-US-00008 TABLE 8 Heat of Lap fusion (J/g shear Std. No. PEEK/PAEK-2 polymer) of Stress dev. Cohesive Failure Example composition composition (psi) (psi) Failures Type C40 C39 41.6 804 107 0/5 Adhesive E41 E37 33.5 1157 71 5/5 2 partially cohesive + 3 specimen breaks E42 E38 30.3 1202 43 5/5 5 specimen breaks

[0242] Referring to TABLE 8, the results demonstrate that for the lap shear samples tested, the compositions according to the invention significantly improve the adhesion to aluminum as compared to PEEK (C45), while retaining a good level of crystallinity (>30 J/g heat of fusion).

Examples C43 -E45

Preparation of Glass-Fiber Reinforced Compositions

[0243] The compositions of comparative Example C43 and Examples E44 and E45, having a 60/40 PEEK (KetaSpire KT-880)/PAEK-2 ratio, as specified in Table 9 below, were prepared by first tumble blending in powder form the polymers to be blended at the desired ratios for about 20 minutes to create a premix of the polymers. This was followed by melt compounding using a 26 mm Coperion co-rotating partially intermeshing twin screw extruder having a length to diameter (L/D) ratio of 48:1. The extruder had 12 barrel sections with barrel sections 2 through 7 being heated with a temperature setting of 350 C. while barrel sections 8-12 and the die were heated to a temperature set point of 360 C. The melt temperature recorded for the extrudate as it exited the die ranged between 394 and 398 C. for all the compositions. The feeding of the extruder was such that the polymer components were metered gravimetrically at the extruder feed hopper, while the glass fiber was metered also using a gravimetric feeder at the proportion corresponding to the 30 wt. % level in each composition at barrel section 7. The extruder was operated at a total throughput rate of 40 lb/hr (18.15 kg/hr) which corresponded to a resin feed rate of 28 lb/hr (12.70 kg/hr) and a glass fiber feed rate of 12 lb/hr (5.44 kg/hr). The extruder screw speed was set at 200 rpm throughout and the extruder torque reading was maintained in the 60-70% range during compounding of all the compositions. Vacuum venting with a vacuum level >25 in Hg was applied at barrel section 10 during compounding to strip off moisture and any possible residual volatiles from the compound. The extrudate from each of the runs was stranded and cooled in a water trough and then pelletized into pellets approximately 2.7 mm in diameter and 3.0 mm in length.

TABLE-US-00009 TABLE 9 PAEK2 Polymer Repeat PAEK2 PEEK PAEK GF PEEK/PAEK2 Composition Unit Source T.sub.m ( C.) wt % 2 wt % wt % wt/wt ratio C43 (J-B) and (J- Cypek 336 42 28 30.0 60/40 B), FC (J-B)/(J-B) > 65/35 E44 (J-B) and (J-B) Cypek NDa 42 28 30.0 60/40 (J-B)/(J-B) = DS-M 55/45-65/35 E45 (J-B) and (J-B) Cypek 310 42 28 30.0 60/40 (J-B)/(J-B) = DS-E 55/45-65/35 a: no melting endotherm detected on the second heat DSC scan

Examples C46 to E48

Adhesion Strength of Compositions C43-E45 to Aluminum

[0244] These Examples demonstrate the adhesion of blends of PEEK =PAEK1 with PAEK2 =PEKK of different crystallinity and T.sub.m. To demonstrate adhesion, lap shear samples were formed and the lap shear stress was measured at room temperature and according to the ASTM D1002 standard with a grip distance of 3.5 inches. Lap shear samples were formed by overmolding the metal substrates with the described PAEK1/PAEK2 compositions. The metal substrates were formed from aluminum 6061 alloy and had a double butt lap joint with a surface area of about 0.25 square inches (In).

[0245] The aluminum substrates were laser etched (Minilase, from Tykma Technologies) to form a crosshatch pattern having a distance of about 100 m between parallel lines. Following etching, the metal substrates were rinsed in acetone or isopropanol and dried in a vacuum oven at about 50 Torr to about 100 Torr and at about 50 C. or 100 C.

[0246] A PAEK1/PAEK2 composition was deposited on the metal substrates using injection molding (pellets pre-dried at 120 C/25 Hg vacuum for 4 hours). In particular, the metal substrates were preheated to a temperature of about 190 C. to about 200 C. in an oven and, subsequently, on a hotplate. The preheated substrates were then placed in an injection mold heated to about 199 C. The PAEK1/PAEK2 composition was then injected, into the mold, at a temperature between from about 370 C. to about 380 C. to form the lap shear samples. The lap shear sample was removed from the mold and allowed to continue to cool to room temperature.

[0247] The lap shear stress values, measured at 0.05 in/minute, listed in TABLE 10 are averaged over the number of lap shear samples in the corresponding Sample Set. The heat of fusion, indicative of the degree of crystallinity of the compositions, derived from the melting endotherm on the 2nd heat scan in DSC at 20 C./minute is also indicated in TABLE 10.

[0248] The results of the lap shear test measurements are reported with respect to lap shear stress at break as well and were further analyzed to determine the type of failure at break. In particular, following failure of the lap shear samples, the samples were analyzed to determine if the failure was Adhesive, Cohesive, Partially Cohesive or Specimen Break. Adhesive failures were characterized by a lack of visually detectable polymer on the metal and lack of visually detectable metal on the polymer, on the fracture surface of the sample. Cohesive failures were characterized by a visually detectable amount of polymer on the metal or a visually detectable amount of metal on the polymer, on the fracture surface of the sample. Partially Cohesive failures were analogous to Cohesive failures but showed a reduced amount of polymer on the metal or metal on the polymer. Specimen Break was characterized by fracture in the bulk polymer and not at the metal/polymer interface.

TABLE-US-00010 TABLE 10 Heat of Lap PEEK/ fusion (J/g) shear No. PAEK2 of Stress Std. dev. Cohesive Example composition composition (psi) (psi) Failures Failure Type C46 C43 44.7 1190 249 5/5 3 partially cohesive + 2 specimen breaks E47 E44 37.7 1330 149 6/6 3 partially cohesive + 3 specimen breaks E48 E45 37.3 1330 95 6/6 3 partially cohesive + 3 specimen breaks

[0249] Referring to TABLE 10, the results demonstrate that for the lap shear samples tested, the compositions with PAEK2=PEKK with T.sub.m<315 C. (i.e. amorphous PEKK) exhibit better adhesion than compositions with PAEK232 PEKK with T.sub.m>315 C. (i.e. crystalline PEKK), while retaining a good level of crystallinity (>30 J/g heat of fusion).