Polymer Composite Containing Recycled Carbon Fibers

Abstract

A polymer composition is described well suited for being combined with relatively short fibers. The fibers, for instance, can have a mean fiber length of less than 1,000 microns, such as less than 700 microns, such as less than 500 microns. The polymer formulation allows for intimate mixing with the fibers without having to use a sizing agent. In one embodiment, the composition contains a polybutylene terephthalate polymer combined with a thermoplastic polymer having lower crystallinity.

Claims

1. A reinforced polymer composition comprising: a first polyester polymer; a second polyester polymer blended with the first polyester polymer, the second polyester polymer being less crystalline than the first polyester polymer, the second polyester polymer being present in the polymer composition in an amount from about 2% by weight to about 35% by weight; and carbon fibers combined with the first and second polyester polymers, the carbon fibers being present in the polymer composition in an amount from about 5% by weight to about 50% by weight, and wherein the carbon fibers have a mean fiber length of from about 10 microns to about 1,000 microns.

2. A reinforced polymer composition as defined in claim 1, wherein the carbon fibers have a mean fiber length of from about 50 microns to about 500 microns.

3. A reinforced polymer composition as defined in claim 1, wherein the carbon fibers have a mean fiber length of from about 50 microns to about 200 microns, and wherein the carbon fibers are present in the composition in an amount from about 10% to about 45% by weight.

4. A reinforced polymer composition as defined in claim 1, wherein the carbon fibers are substantially free of a sizing agent.

5. A reinforced polymer composition as defined in claim 1, wherein the first polyester polymer has a crystallinity of greater than about 40%.

6. A reinforced polymer composition as defined in claim 1, wherein the second polyester polymer has a crystallinity of less than about 40%.

7. A reinforced polymer composition as defined in claim 1, wherein the first polyester polymer comprises polybutylene terephthalate.

8. A reinforced polymer composition as defined in claim 1, wherein the second polyester polymer comprises polyethylene terephthalate.

9. A reinforced polymer composition as defined in claim 1, wherein the composition further contains a fatty acid ester.

10. A reinforced polymer composition as defined in claim 9, wherein the fatty acid ester comprises an ester of montanic acid.

11. A reinforced polymer composition as defined in claim 1, wherein the composition further contains a nucleating agent.

12. A reinforced polymer composition as defined in claim 11, wherein the nucleating agent comprises talc and wherein the nucleating agent is present in the composition in an amount from about 0.001% to about 0.5% by weight.

13. A reinforced polymer composition as defined in claim 1, wherein the composition contains a heat stabilizer and an antioxidant.

14. A reinforced polymer composition as defined in claim 13, wherein the heat stabilizer comprises a diphosphate or triphosphite and wherein the antioxidant comprises a sterically hindered phenolic compound.

15. A reinforced polymer composition as defined in claim 1, wherein the composition is in a compounded form.

16. A reinforced polymer composition comprising: a polyester polymer comprising a polybutylene terephthalate polymer; a fatty acid ester blended with the polyester polymer; a nucleant blended with the polyester polymer; a heat stabilizing agent and an antioxidant blended with the polyester polymer; and carbon fibers combined with the polyester polymer, the carbon fibers being present in the polymer composition in an amount from about 5% to about 50% by weight, the carbon fibers having a mean fiber length of from about 50 microns to about 500 microns.

17. A reinforced polymer composition as defined in claim 16, further comprising a second polyester polymer, the second polyester polymer being less crystalline than the polybutylene terephthalate polymer.

18. A reinforced polymer composition as defined in claim 16, wherein the fatty acid ester comprises an ester of montanic acid.

19. A reinforced polymer composition as defined in claim 16, wherein the nucleating agent comprises talc and wherein the nucleating agent is present in the composition in an amount from about 0.001% to about 0.5% by weight.

20. A reinforced polymer composition as defined in claim 16, wherein the heat stabilizer comprises a diphosphate or triphosphite and wherein the antioxidant comprises a sterically hindered phenolic compound.

21. A reinforced polymer composition as defined in claim 16, wherein the polybutylene terephthalate polymer is present in the composition in an amount from about 20% to about 90% by weight.

22. A housing comprising: a molded polymer article defining a casing for enclosing an adjacent structure, the molded polymer article being made from a polymer composition comprising a first polyester polymer comprising polybutylene terephthalate and a second polyester polymer that is less crystalline than the first polyester polymer blended with the carbon fibers, the carbon fibers having a mean fiber length of from about 10 microns to about 1,000 microns, the polymer composition having a tensile strength of greater than 110 MPa, having a tensile modulus of greater than about 12,000 MPa, and having an elongation at break of greater than about 2%.

23. A housing as defined in claim 22, wherein the housing is part of an automobile engine.

24. A housing as defined in claim 22, wherein the housing is part of a windshield wiper assembly.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0018] A full and enabling disclosure of the present disclosure is set forth more particularly in the remainder of the specification, including reference to the accompanying figures, in which:

[0019] FIG. 1 is a perspective view of a vehicle engine illustrating various molded polymer parts that may be made in accordance with the present disclosure.

[0020] Repeat use of reference characters in the present specification and drawings is intended to represent the same or analogous features or elements of the present invention.

DETAILED DESCRIPTION

[0021] It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present disclosure.

[0022] The present disclosure is generally directed to fiber reinforced polymer compositions containing relatively short reinforcing fibers. The polymer composition of the present disclosure, for instance, is particularly well suited to incorporating recycled carbon fibers into the polymer matrix. Of particular advantage, the polymer composition of the present disclosure can synergistically combine with the carbon fibers in a manner that produces products having a good combination of physical properties without having to apply a sizing agent to the fibers.

[0023] In general, the polymer composition of the present disclosure contains at least one polyester polymer blended with relatively short fibers. The fibers, for instance, can have a mean fiber length of less than about 1,000 microns, such as less than about 700 microns, such as less than about 500 microns, such as less than about 400 microns, such as even less than about 100 microns. The fibers generally have a length of greater than about 10 microns, such as greater than about 50 microns. For example, the mean fiber length before compounding may be less than about 700 microns, such as less than about 500 microns, and also greater than about 100 microns. After compounding, the mean fiber length may be, for example, less than about 500 microns, such as less than about 400 microns, such as less than about 200 microns.

[0024] As used herein, the mean fiber length is determined generally according to ISO Test No. 22314 (First Edition, May 1, 2006). However, as used herein, the fiber length is determined semiautomatically. In particular, magnified images according to Section 6.3 of ISO Test 22314 are captured with a high resolution scanner and analyzed using IMAGE PRO PLUS picture analysis software. Three to five frames are evaluated for each sample. The determination of the length of the individual fibers is done in an automated way by the above software.

[0025] The at least one polyester polymer comprises a polybutylene terephthalate. In one embodiment, the polybutylene terephthalate is combined with a second thermoplastic polymer. The second thermoplastic polymer may also comprise a polyester polymer. The second thermoplastic polymer has a lower crystallinity than the polybutylene terephthalate. The polymer composition can also contain various other components such as a nucleant, a fatty acid ester, and one or more stabilizing agents and/or antioxidants.

[0026] The polymer composition of the present disclosure is well suited to being formed into various different polymer articles, including parts and products. In one embodiment, for instance, the polymer composition may be used to produce automotive parts, such as housings.

[0027] Referring to FIG. 1, for instance, various polymer articles made in accordance with the present disclosure are shown. For example, in one embodiment, the polymer composition can be used to produce housings 10, 12 and 14. The housings have a shape so as to enclose an adjacent structure. In FIG. 1, for instance, housing 10 comprises an engine cover.

[0028] In other embodiments, the housing can be used to enclose a motor or other component. In one embodiment, for instance, as shown in FIG. 1, the housing 16 can be part of a wiper blade assembly. The housing can be used to cover the motor of the wiper blade or can be used to cover a portion of the wiper blade itself.

[0029] In still another embodiment, the housing may be used to cover a motor of a power window assembly.

[0030] When used to construct a housing as described above, the polymer composition of the present disclosure can have a desired balance of properties. For instance, the polymer composition can have a tensile strength of greater than about 110 MPa, such as greater than about 120 MPa, such as greater than about 130 MPa, such as greater than about 140 MPa, such as greater than about 150 MPa, such as even greater than about 180 MPa, or even greater than about 200 MPa. The tensile strength of the polymer composition is generally less than about 350 MPa. The polymer composition can have a tensile modulus of greater than about 12,000 MPa, such as greater than about 12,500 MPa, such as greater than about 13,000 MPa, such as greater than about 14,000 MPa, such as greater than about 15,000 MPa, such as greater than about 16,000 MPa, such as greater than about 17,000 MPa, such as greater than about 18,000 MPa, such as even greater than about 20,000 MPa. The tensile modulus is generally less than about 40,000 MPa, such as less than about 35,000 MPa. Of particular advantage, the polymer composition can have the above tensile strength and tensile modulus properties while having desired elongation properties. For instance, the polymer composition may display an elongation at break of greater than about 2%, such as greater than about 2.3%, such as greater than about 2.5%, such as greater than about 2.8%, such as greater than about 3%, such as greater than about 3.5%, such as even greater than about 4%. The elongation at break is generally less than about 10%, such as less than about 8%.

[0031] In one embodiment, the composition comprises a first polyester polymer and a second polyester polymer having a lower crystallinity than the first polyester polymer. It has been found that incorporating a second, less crystalline polyester to a composition containing a first, more crystalline polyester and carbon fibers improves the mechanical properties of the composition. Of particular advantage, when this combination is used, the mechanical properties of a carbon fiber reinforced polyester can be improved without the use of a sizing agent on the carbon fibers.

[0032] The polyesters which are suitable for use herein are derived from an aliphatic or cycloaliphatic diol, or mixtures thereof, containing from 2 to about 10 carbon atoms and an aromatic dicarboxylic acid, i.e., polyalkylene terephthalates.

[0033] The polyesters which are derived from a cycloaliphatic diol and an aromatic dicarboxylic acid are prepared by condensing either the cis- or trans-isomer (or mixtures thereof) of, for example, 1,4-cyclohexanedimethanol with the aromatic dicarboxylic acid.

[0034] Examples of aromatic dicarboxylic acids include isophthalic or terephthalic acid, 1,2-di(p-carboxyphenyl)ethane, 4,4-dicarboxydiphenyl ether, etc., and mixtures of these. Ail of these acids contain at least one aromatic nucleus. Fused rings can also be present such as in 1,4- or 1,5- or 2,6-naphthalene-dicarboxylic acids. In one embodiment, the dicarboxylic acid is terephthalic acid or mixtures of terephthalic and isophthalic acid.

[0035] Polyesters that may be used in the polymer composition, for instance, include polyethylene terephthalate, polybutylene terephthalate, mixtures thereof and copolymers thereof.

[0036] As described above, the composition may comprise a first polyester and a second polyester with a lower crystallinity than the first polyester. For example, the first polyester may have a crystallinity greater than about 40%, such as greater than about 45%. The second, less crystalline polyester may have a crystallinity less than about 40%, such as less than about 35%.

[0037] Percent crystallinity may be determined using differential scanning calorimetry (DSC). Such analysis may be performed using a Pyris 6 DSC from PerkinElmer instruments. A detailed description of the calculation is available from Sichina, W. J. DSC as problem solving tool: measurement of percent crystallinity of thermoplastics. Thermal Analysis Application Note (2000).

[0038] Those skilled in the art will appreciate that the degree of crystallinity of a given polyester may depend upon the monomers used to form the polymer, the process temperatures during formation of the polymer, the process used to make the polymer, and/or the molecular structure of the polyester. In one embodiment, the degree of crystallinity of a polyester can be altered by changing the amount and/or type and/or distribution of monomer units that make up the polyester chain. For example, if about 3 to about 15 mole percent of the ethylene glycol repeat units in poly ethylene terephthalate are replaced with 1,4-cyclohexanedimethanol repeat units, or by di-ethylene glycol repeat units, the resulting modified polyester can be amorphous and has a low melt processing temperature. Similarly, if about 10 to about 20 mole percent of the terephthalic acid repeat units in polyethylene terephthalate (or polybutylene terephthalate) are replaced with isophthalic acid repeat units, the resulting modified polyester can also be amorphous and have a low melt processing temperature. Such concepts can also be combined into one polyester or by melt mixing at least two different polyesters. Accordingly, the choice of a particular modifying acid or dial can significantly affect the melt processing properties of the polyester.

[0039] As used herein, the terms modifying acid and modifying diol are meant to define compounds, which can form part of the acid and diol repeat units of a polyester, respectively, and which can modify a polyester to reduce its crystallinity or render the polyester amorphous. In one embodiment, however, the polyesters present in the polymer composition of the present disclosure are non-modified and do not contain a modifying acid or a modifying dial.

[0040] Examples of modifying acid components may include, but are not limited to, isophthalic acid, phthalic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 2,6-naphthaline dicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, suberic acid, 1,12-dodecanedioic acid, and the like. In practice, it is often preferable to use a functional acid derivative thereof such as the dimethyl, diethyl, or dipropyl ester of the dicarboxylic acid. The anhydrides or acid halides of these acids also may be employed where practical. Preferred is isophthalic acid.

[0041] Examples of modifying diol components may include, but are not limited to, neopentyl glycol, 1,4-cyclohexanedimethanol, 1,2-propanediol, 1,3-propanediol, 2-Methy-1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 2,2,4,4-tetramethyl 1,3-cyclobutane diol, Z,8-bis(hydroxymethyltricyclo-[5.2.1.0]-decane wherein Z represents 3, 4, or 5; 1,4-Bis(2-hydroxyethoxy)benzene, 4,4-Bis(2-hydroxyethoxy) diphenylether [Bis-hydroxyethyl Bisphenol A], 4,4-Bis(2-hydroxyethoxy)diphenylsulfide [Bis-hydroxyethyl Bisphenol S] and diols containing one or more oxygen atoms in the chain, e.g. diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, and the like. In general, these diols contain 2 to 18, preferably 2 to 8 carbon atoms. Cycloalphatic diols can be employed in their cis or trans configuration or as mixtures of both forms.

[0042] Other suitable low melt processing polyesters are based on polyaddition of lactones, for example poly-c-caprolacton.

[0043] The at least one polyester or copolyester present in the composition can generally have an intrinsic viscosity (IV) of from about 0.5 to about 0.9 dL/g, such as from about 0.5 to about 0.8 dL/g. In one embodiment, for instance, the intrinsic viscosity of the polyester is from about 0.65 to about 0.8 dL/g.

[0044] The at least one polyester is present in the polymer composition in an amount sufficient to form a continuous phase. For example, the polyester may be present in the polymer composition in an amount of at least about 25% by weight, such as in an amount of at least about 30% by weight, such as in an amount of at least 35% by weight, such as in an amount of at least about 40% by weight, such as at least about 50% by weight, such as at least about 60% by weight. The thermoplastic polymer is generally present in an amount less than about 95% by weight.

[0045] When using a first polyester and a second polyester having a lower crystallinity than the first polyester, the first polyester may be present in an amount greater than about 25% by weight, such as greater than about 40% by weight. The first polyester is generally present in an amount less than about 93% by weight. The second polyester may be present in an amount less than 50% by weight, such as less than 40% by weight, preferably between about 2% to about 35% by weight.

[0046] In a particularly preferred embodiment, the first polyester is polybutylene terephthalate (PBT) and the second, less crystalline polyester is polyethylene terephthalate (PET). The polybutylene terephthalate may have a crystallinity of greater than about 38%, such as greater than about 40%, such as greater than about 45%. The crystallinity of the polybutylene terephthalate is generally less than about 70%. The polyethylene terephthalate, on the other hand, can have a crystallinity of less than about 40%, such as less than about 38%, such as less than about 35%, such as less than 32%. The crystallinity of the polyethylene terephthalate is generally greater than 0%, such as greater than 5%.

[0047] The polymer composition can also have excellent impact resistance. For instance, when tested according to the notched Charpy test at 23 C., the polymer composition may have an impact resistance of at least about 25 kJ/m.sup.2, such as at least about 30 kJ/m.sup.2, such as at least about 35 kJ/m.sup.2, such as at least about 40 kJ/m.sup.2, such as at least about 45 kJ/m.sup.2, such as at least about 50 kJ/m.sup.2 (generally less than 65 kJ/m.sup.2, such as less than 60 kJ/m.sup.2). It has been surprisingly found that when a less crystalline polyester is incorporated into a composition including a more crystalline polyester and carbon fibers, the impact strength is improved. 16270780In accordance with the present disclosure, a composition is provided which includes a blend of a first polyester and a second less crystalline polyester present in a weight ratio in the range of about 50:1 to 5:7, preferably between about 5:1 and 3:4, even more preferably between about 5:1 to 8:5, said blend of first polyester and second polyester present in a concentration in the ratio of between about 55% and 95% by weight, preferably between about 60% and 90% by weight based on the total weight of the composition. The composition includes carbon fibers generally in an amount greater than about 5% by weight, such as in an amount greater than about 8% by weight, such as in an amount greater than about 10% by weight, such as in an amount greater than about 12% by weight, such as in an amount greater than about 15% by weight. The carbon fibers are present in the polymer composition generally in an amount less than about 45% by weight, such as in an amount less than about 40% by weight, such as in an amount less than about 35% by weight, such as in an amount less than about 30% by weight.

[0048] The carbon fibers present in the composition can be recycled carbon fibers. For example, carbon fibers which have been formed into a carbon fiber fabric, but which have not been impregnated by a polymer, may be broken down into individual carbon fibers, especially short carbon fibers. An example of a process for recycling carbon fibers into short carbon fiber lengths is disclosed by German Patent Application DE 102009023529, which is incorporated herein by reference.

[0049] The carbon fibers present in the composition can be short carbon fibers having a mean fiber length up to about 1,000 microns. In one embodiment, the carbon fibers have a mean fiber length of up to about 700 microns, such as between about 50 microns and 500 microns. For example, the mean fiber length before compounding may be less than about 700 microns, such as less than about 500 microns, and also greater than about 100 microns. After compounding, the mean fiber length may be, for example, less than about 500 microns, such as less than about 400 microns, such as less than about 300 microns. In another embodiment, carbon fibers having a mean length from about 50 to about 500 microns and are present in the composition in an amount from about 8% to about 35% by weight based on the total weight of the composition.

[0050] In addition to the at least one polyester and the carbon fibers, the composition may also contain any number of desired additives,

[0051] For example, the composition may further include a nucleating agent, present in a concentration of between about 0.1 and 2% by weight, preferably between about 0,001% and 0.5% based on the total weight of the composition. The nucleating agent can be selected from the group consisting of alkali metal salts having anions which are oxides of the elements from Group IV of the Periodic Table; barium sulfate; and talc.

[0052] The polymer composition may also contain at least one stabilizer. The stabilizer may comprise an antioxidant, a light stabilizer such as an ultraviolet light stabilizer, a thermal stabilizer, and the like.

[0053] Sterically hindered phenolic antioxidant(s) may be employed in the composition. Examples of such phenolic antioxidants include, for instance, calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate) (Irganox 1425); terephthalic acid, 1,4-dithio-,S,S-bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) ester (Cyanox 1729); triethylene glycol bis(3-tert-butyl-4-hydroxy-5-methylhydrocinnamate); hexamethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate (Irganox 259); 1,2-bis(3,5,di-tert-butyl-4-hydroxyhydrocinnamoyphydrazide (Irganox 1024); 4,4-di-tert-octyldiphenamine (Naugalube 438R); phosphonic add, (3,5-di-tert-butyl-4-hydroxybenzyl)-,dioctadecyl ester (Irganox 1093); 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4 hydroxybenzyl)benzene (Irganox 1330); 2,4-bis(octylthio)-8-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine (Irganox 565); isooctyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox 1135); octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox 1076); 3,7-bis(1,1,3,3-tetramethylbutyl)-10H-phenothiazine (Irganox LO 3); 2,2-methylenebis(4-methyl-6-tert-butylphenol)monoacrylate (Irganox 3052); 2-tert-butyl-6-[1-(3-tert-butyl-2-hydroxy-5-methylphenyl)ethyl]-4-methylphenyl acrylate (Sumilizer TM 4039); 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate (Sumilizer GS); 1,3-dihydro-2H-Benzimidazole (Sumilizer MB); 2-methyl4,6-bis[(octylthio)methyl]phenol (Irganox 1520); N,N-trimethylenebis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide (Irganox 1019); 4-n-octadecyloxy-2,6-diphenylphenol (Irganox 1063); 2,2-ethylidenebis[4,6-di-tert-butylphenol] (Irganox 129); N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamide) (Irganox 1098); diethyl (3,5-di-tert-butyl-4-hydroxybenxyl)phosphonate (Irganox 1222); 4,4-di-tert-octyldiphenylamine (Irganox 5057); N-phenyl-1-napthalenamine (Irganox L 05); tris[2-tert-butyl-4-(3-ter-butyl-4-hydroxy-6-methylphenylthio)-5-methyl phenyl]phosphite (Hostanox OSP 1); zinc dinonyidithiocarbamate (Hostanox VP-ZNCS 1); 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane AG80); pentaerythrityl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox 1010); ethylene-bis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)-propionate (Irganox 245); 3,5-di-tert-butyl-4-hydroxytoluene (Lowinox BHT, Chemtura) and so forth.

[0054] Some examples of suitable sterically hindered phenolic antioxidants for use in the present composition are triazine antioxidants having the following general formula:

##STR00001##

wherein, each R is independently a phenolic group, which may be attached to the triazine ring via a C.sub.1 to C.sub.5 alkyl or an ester substituent. Preferably, each R is one of the following formula (I)-(III):

##STR00002##

[0055] Commercially available examples of such triazine-based antioxidants may be obtained from American Cyanamid under the designation Cyanox 1790 (wherein each R group is represented by the Formula III) and from Ciba Specialty Chemicals under the designations Irganox 3114 (wherein each R group is represented by the Formula I) and Irganox 3125 (wherein each R group is represented by the Formula II).

[0056] Sterically hindered phenolic antioxidants may constitute from about 0.01 wt. % to about 3 wt. %, in some embodiments from about 0.05 wt. % to about 1 wt. %, and in some embodiments, from about 0.05 wt. % to about 0.1 wt. % of the entire stabilized polymer composition. In one embodiment, for instance, the antioxidant comprises pentaerythrityl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

[0057] Hindered amine light stabilizers (HALS) may be employed in the composition to inhibit degradation of the polyester composition and thus extend its durability. Suitable HALS compounds may be derived from a substituted piperidine, such as alkyl-substituted piperidyl, piperidinyl, piperazinone, alkoxypiperidinyl compounds, and so forth. For example, the hindered amine may be derived from a 2,2,6,6-tetraalkylpiperidinyl. Regardless of the compound from which it is derived, the hindered amine is typically an oligomeric or polymeric compound having a number average molecular weight of about 1,000 or more, in some embodiments from about 1000 to about 20,000, in some embodiments from about 1500 to about 15,000, and in some embodiments, from about 2000 to about 5000. Such compounds typically contain at least one 2,2,6,6-tetraalkylpiperidinyl group (e.g., 1 to 4) per polymer repeating unit.

[0058] Without intending to be limited by theory, it is believed that high molecular weight hindered amines are relatively thermostable and thus able to inhibit light degradation even after being subjected to extrusion conditions. One particularly suitable high molecular weight hindered amine has the following general structure:

##STR00003##

wherein, p is 4 to 30, in some embodiments 4 to 20, and in some embodiments 4 to 10. This oligomeric compound is commercially available from Clariant under the designation Hostavin N30 and has a number average molecular weight of 1200.

[0059] Another suitable high molecular weight hindered amine has the following structure:

##STR00004##

wherein, n is from 1 to 4 and R.sub.30 is independently hydrogen or CH.sub.3. Such oligomeric compounds are commercially available from Adeka Palmarole SAS (joint venture between Adeka Corp. and Palmarole Group) under the designation ADK STAB LA-63 (R.sub.30 is CH.sub.3) and ADK STAB LA-68 (R.sub.30 is hydrogen).

[0060] Other examples of suitable high molecular weight hindered amines include, for instance, an oligomer of N-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol and succinic acid (Tinuvin 622 from Ciba Specialty Chemicals, MW=4000); oligomer of cyanuric acid and N,N-di(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylene diamine; poly((6-morpholine-S-triazine-2,4-diyl)(2,2,6,6-tetramethyl-4-piperidinyl)-iminohexamethylene-(2,2,6,6-tetramethyl-4-piperidinyl)-imino) (Cyasorb UV 3346 from Cytec, MW=1600); polymethylpropyl-3-oxy-[4(2,2,6,6-tetramethyl)-piperidinylysiloxane (Uvasil 299 from Great Lakes Chemical, MW=1100 to 2500); copolymer of -methylstyrene-N-(2,2,6,6-tetramethyl-4-piperidinyl)maleimide and N-stearyl maleimide: 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol tetramethyl-polymer with 1,2,3,4-butanetetracarboxylic acid; and so forth. Still other suitable high molecular weight hindered amines are described in U.S. Pat. No. 5,679,733 to Malik, et al. and U.S. Pat. No. 6,414,155 to Sassi, et al., which are incorporated herein in their entirety by reference thereto for all purposes.

[0061] In addition to the high molecular hindered amines, low molecular weight hindered amines may also be employed in the composition. Such hindered amines are generally monomeric in nature and have a molecular weight of about 1000 or less, in some embodiments from about 155 to about 800, and in some embodiments, from about 300 to about 800.

[0062] Specific examples of such low molecular weight hindered amines may include, for instance, bis-(2,2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin 770 from Ciba Specialty Chemicals, MW-481); bis-(1,2,2,6,6-pentamethyl-4-piperidinyl)-(3,5-ditert,butyl-4-hydroxybenzyl)butyl-propane dioate; bis-(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate; 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro-(4,5)-decane-2,4-dione, butanedioic acid-bis-(2,2,6.sub.26-tetramethyl-4-piperidinyl) ester; tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate; 7-oxo-3,20-diazadispiro(5.1.11.2) beneicosan-20-propanoic acid, 2,2,4,4-tetramethyl-21-oxo, dodecyl ester; N-(2,2,6,6-tetramethyl-4-piperidinyl)-N-amino-oxamide; o-t-amyl-o-(1,2,2,6,6-pentamethyl-4-piperidinyl)-monoperoxi-carbonate; -alanine, N-(2,2,6,6-tetramethyl-4-piperidinyl), dodecylester; ethanediamide, N-(1-acetyl-2,2,6,6-tetramethylpiperidinyl)-N-dodecyl; 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidinyl)-pyrrolidin-2,5-dione; 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidinyl)-pyrrolidin-2,5-dione; 3-dodecyl-1-(1-acetyl,2,2,6,6-tetramethyl-4-piperidinyl)-pyrrolidin-2,5-dione, (Sanduvar 3058 from Clariant, MW=448.7); 4-benzoyloxy-2,2,6,6-tetramethylpiperidine; 1-[2-(3,5-di-tert-butyl-4-hydroxyphenylpropionyloxy)ethyl]-4-(3,5-di-tert-butyl-4-hydroxylphenyl propionyloxy)-2,2,6,6-tetramethyl-piperidine; 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidinylamino)-N-(2,2,6,6-tetra-methyl-4-piperidinyl)propionylamide; 1,2-bis-(3,3,5,5-tetramethyl-2-oxo-piperazinyl)ethane; 4-oleoyloxy-2,2,6,6-tetramethylpiperidine; and combinations thereof. Other suitable low molecular weight hindered amines are described in U.S. Pat. No. 5,679,733 to Malik, et al,

[0063] The hindered amines may be employed singularly or in combination in any amount to achieve the desired properties, but typically constitute from about 0.01 wt. % to about 4 wt. % of the polymer composition.

[0064] UV absorbers, such as benzotriazoles or benzopheones, may be employed in the composition to absorb ultraviolet light energy. Suitable benzotriazoles may include, for instance, 2-(2-hydroxyphenyl)benzotriazoles such as 2-(2-hydroxy-5-methylphenyl)benzotriazole; 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole (Cyasorb UV 5411 from Cytec); 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzo-triazole; 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole; 2-(2-hydroxy-3,5-dicumylphenyl)benzotriazole; 2,2-methylenebis(4-tert-octyl-6-benzo-triazolylphenol); polyethylene glycol ester of 2-(2-hydroxy-3-tert-butyl-5-carboxyphenyl)benzotriazole; 2-[2-hydroxy-3-(2-acryloyloxyethyl)-5-methylphenyl]-benzotriazole; 2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert-butylphenyl]benzotriazole; 2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert-octylphenyl]benzotriazole; 2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert-butylphenyl]-5-chlorobenzotriazole; 2-[2-hydroxy-5-(2-methacryloyloxyethyl)phenyl]benzotriazole; 2-[2-hydroxy-3-tert-butyl-5-(2-methacryloyloxyethyl)phenyl]benzotriazole; 2-[2-hydroxy-3-tert-amyl-5-(2-methacryloyloxyethyl)phenyl]benzotriazole; 2-[2-hydroxy-3-tert-butyl-5-(3-methacryloyloxypropyl)phenyl]-5-chlorobenzotriazole; 2-[2-hydroxy-4-(2-methacryloyloxymethyl)phenyl]benzotriazole; 2-[2-hydroxy-4-(3-methacryloyloxy-2-hydroxypropyl)phenyl]benzotriazole; 2-[2-hydroxy-4-(3-methacryloyloxypropyl)phenyl]benzotriazole; and combinations thereof.

[0065] Exemplary benzophenone light stabilizers may likewise include 2-hydroxy-4-dodecyloxybenzophenone; 2,4-dihydroxybenzophenone; 2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate (Cyasorb UV 209 from Cytec); 2-hydroxy-4-n-octyloxy)benzophenone (Cyasorb 531 from Cytec); 2,2-dihydroxy-4-(octyloxy)benzophenone (Cyasorb UV 314 from Cytec); hexadecyl-3,5-bis-tert-butyl-4-hydroxybenzoate (Cyasorb UV 2908 from Cytec); 2,2-thiobis(4-tert-octylphenolato)-n-butylamine nickel(II) (Cyasorb UV 1084 from Cytec); 3,5-di-tert-butyl-4-hydroxybenzoic acid, (2,4-di-tert-butylphenyl)ester (Cyasorb 712 from Cytec); 4,4-dimethoxy-2,2 -dihydroxybenzophenone (Cyasorb UV 12 from Cytec); and combinations thereof.

[0066] When employed, UV absorbers may constitute from about 0.01 wt. % to about 4 wt. % of the entire polymer composition.

[0067] In one embodiment, the polymer composition may contain a blend of stabilizers that produce ultraviolet resistance and color stability. The combination of stabilizers may allow for products to be produced that have bright and fluorescent colors. In addition, bright colored products can be produced without experiencing significant color fading over time. In one embodiment, for instance, the polymer composition may contain a combination of a benzotriazole light stabilizer and a hindered amine light stabilizer, such as an oligomeric hindered amine.

[0068] Various other stabilizers may also be present in the composition. For instance, in one embodiment, the composition may contain a phosphite, such as a diphosphite. For instance, in one embodiment, the phosphite compound may comprise distearyl pentaerythritol diphosphite. The phosphite compound may also comprise bis(2,4-ditert-butylphenyl)pentaerythritol diphosphite.

[0069] Organophosphorus compounds may be employed in the composition that serve as secondary antioxidants to decompose peroxides and hydroperoxides into stable, non-radical products. Trivalent organophosphorous compounds (e.g., phosphites or phosphorites) are particularly useful in the stabilizing system of the present invention. Monophosphite compounds only one phosphorus atom per molecule) may be employed in certain embodiments of the present invention. Preferred monophosphites are aryl monophosphites contain C.sub.1 to C.sub.10 alkyl substituents on at least one of the aryloxide groups. These substituents may be linear (as in the case of nonyl substituents) or branched (such as isopropyl or tertiary butyl substituents). Non-limiting examples of suitable aryl monophosphites (or monophosphonites) may include triphenyl phosphite; diphenyl alkyl phosphites; phenyl dialkyl phosphites; tris(nonylphenyl) phosphite (Weston 399, available from GE Specialty Chemicals); tris(2,4-di-tert-butylphenyl) phosphite (Irgafos 168, available from Ciba Specialty Chemicals Corp.): bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite (Irgafos 38, available from Ciba Specialty Chemicals Corp.); and 2,2,2-nitrilo[triethyltris(3,3,5,5-tetra-tert-butyl-1,1-biphenyl-2,2-diyl) phosphate (Irgafos 12, available from Ciba Specialty Chemicals Corp.). Aryl diphosphites or diphosphonites (i.e., contains at least two phosphorus atoms per phosphite molecule may also be employed in the stabilizing system and may include, for instance, distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, bis(2,4 di-tert-butylphenyl) pentaerythritol diphosphite (Ultranox 626, available from GE Specialty Chemicals); bis(2,6-di-tert-butyl-4-methylpenyl)pentaerythritol diphosphite; bisisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4-biphenylene-diphosphonite (Sandostab P-EPQ, available from Clariant) and bis(2,4-dicumylphenyl)pentaerythritol diphosphite (Doverphos S-9228)

[0070] Organophosphorous compounds may constitute from about 0.01 wt. % to about 2 wt. %, in some embodiments from about 0.05 wt. % to about 1 wt. %, and in some embodiments, from about 0.1 wt. % to about 0.5 wt. % of the polymer composition.

[0071] In addition to those mentioned above, secondary amines may also be employed in the composition. The secondary amines may be aromatic in nature, such as N-phenyl naphthylamines (e.g., Naugard PAN from Uniroyal Chemical); diphenylamines, such as 4,4-bis(dimethylbenzyl)-diphenylamine (e.g., Naugard 445 from Uniroyal Chemical); p-phenylenediamines (e.g., Wingstay 300 from Goodyear); quinolones, and so forth. Particularly suitable secondary amines are oligomeric or polymeric amines, such as homo- or copolymerized polyamides. Examples of such polyamides may include nylon 3 (poly-alanine), nylon 6, nylon 10, nylon 11, nylon 12, nylon 6/6, nylon 6/9, nylon 6/10, nylon 6/11, nylon 6/12, polyesteramide, polyamideimide, polyacrylamide, and so forth. In one particular embodiment, the amine is a polyimide terpolymer having a melting point in the range from 120 C. to 220 C. Suitable terpolymers may be based on the nylons selected from the group consisting of nylon 6, nylon 6/6, nylon 6/9, nylon 6/10 and nylon 6/12, and may include nylon 6-66-69; nylon 6-66-610 and nylon 6-66-612, One example of such a nylon terpolymer is a terpolymer of nylon 6-66-610 and is commercially available from Du Pont de Nemours under the designation Elvamide 8063R. Still other suitable amine compounds are described in U.S. Patent Application Publication No. 2003/0060529 to Ho, et al., which is incorporated herein in its entirety by reference thereto for all purposes.

[0072] Secondary amines may constitute from about 0.01 wt. % to about 2 wt. %, of the entire polymer composition.

[0073] If desired, other known stabilizers may also be incorporated into the composition, such as metal deactivators, acid stabilizers, other light stabilizers (e.g., benzophenones) or antioxidants, etc. Acid stabilizers, for instance, may help neutralize the acidic catalysts or other components present in the polymers. Suitable acid stabilizers may include zinc oxide, calcium lactate, natural and synthetic hydrotalcites, natural and synthetic hydrocalumites, and alkali metal salts and alkaline earth metal salts of higher fatty acids, such as calcium stearate, zinc stearate, magnesium stearate, sodium stearate, sodium ricinoleate and potassium palmitate. When employed, such add stabilizers typically constitutes about 1.5 wt. % or less, in some embodiments, about 1 wt. % or less, and in some embodiments, from about 0.01 wt. % to about 0.5 wt. % of the polymer composition.

[0074] Each stabilizer above may be present in an amount from about 0.01% to about 3% by weight, such as from about 0.05% to about 0.5% by weight. In a preferred embodiment, the composition contains both a heat stabilizer and an antioxidant. For example, the heat stabilizer may comprise a sterically hindered phenolic compound and the antioxidant may comprise a diphosphite.

[0075] In addition to any stabilizer present in the composition, the thermoplastic copolyester composition of the present invention may also include a lubricant that constitutes from about 0.01 wt. % to about 2 wt. %, in some embodiments from about 0.1 wt. % to about 1 wt. %, and in some embodiments, from about 0.2 wt. % to about 0.5 wt. % of the polymer composition. The lubricant may be formed from a fatty add salt derived from fatty adds having a chain length of from 22 to 38 carbon atoms, and in some embodiments, from 24 to 36 carbon atoms. Examples of such fatty adds may include long chain aliphatic fatty adds, such as montanic add (octacosanoic add), arachidic add (arachic add, icosanic add, icosanoic add, n-icosanoic add), tetracosanoic add (lignoceric add), behenic add (docosanoic add), hexacosanoic add (cerotinic add), melissic add (triacontanoic add), erucic add, cetoleic add, brassidic add, selacholeic add, nervonic add, etc. For example, montanic add has an aliphatic carbon chain of 28 atoms and arachidic add has an aliphatic carbon chain of 20 atoms. Due to the long carbon chain provided by the fatty add, the lubricant has a high thermostability and low volatility. This allows the lubricant to remain functional during formation of the desired article to reduce internal and external friction, thereby reducing the degradation of the material caused by mechanical/chemical effects.

[0076] The fatty add salt may be formed by saponification of a fatty add wax to neutralize excess carboxylic adds and form a metal salt. Saponification may occur with a metal hydroxide, such as an alkali metal hydroxide (e.g., sodium hydroxide) or alkaline earth metal hydroxide (e.g., calcium hydroxide). The resulting fatty acid salts typically include an alkali metal (e.g., sodium, potassium, lithium, etc.) or alkaline earth metal (e.g., calcium, magnesium, etc.). Such fatty acid salts generally have an add value (ASTM D 1386) of about 20 mg KOH/g or less, in some embodiments about 18 mg KOH/g or less, and in some embodiments, from about 1 to about 15 mg KOH/g. Particularly suitable fatty add salts for use in the present invention are derived from crude montan wax, which contains straight-chain, unbranched monocarboxylic adds with a chain length in the range of C.sub.28-C.sub.32. Such montanic add salts are commercially available from Clariant GmbH under the designations Licomont CaV 102 (calcium salt of long-chain, linear montanic adds) and Licomont NaV 101 (sodium salt of long-chain, linear montanic adds).

[0077] If desired, fatty add esters may be used as lubricants. Fatty add esters may be obtained by oxidative bleaching of a crude natural wax and subsequent esterification of the fatty adds with an alcohol. The alcohol typically has 1 to 4 hydroxyl groups and 2 to 20 carbon atoms. When the alcohol is multifunctional (e.g., 2 to 4 hydroxyl groups), a carbon atom number of 2 to 8 is particularly desired. Particularly suitable multifunctional alcohols may include dihydric alcohol (e.g., ethylene glycol, propylene glycol, butylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol and 1,4-cyclohexanediol), trihydric alcohol (e.g., glycerol and trimethylolpropane), tetrahydric alcohols (e.g., pentaerythritol and erythritol), and so forth. Aromatic alcohols may also be suitable, such as o-, m- and p-tolylcarbinol, chlorobenzyl alcohol, bromobenzyl alcohol, 2,4-dimethylbenzyl alcohol, 3,5-dimethylbenzyl alcohol, 2,3,5-cumobenzyl alcohol, 3,4,5-trimethylbenzyl alcohol, p-cuminyl alcohol, 1,2-phthalyl alcohol, 1,3-bis(hydroxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, pseudocumenyl glycol, mesitylene glycol and mesitylene glycerol. Particularly suitable fatty add esters for use in the present invention are derived from montanic waxes. Licowax OP (Clariant), for instance, contains montanic adds partially esterified with butylene glycol and montanic acids partially saponified with calcium hydroxide. Thus, Licowax OP contains a mixture of montanic add esters and calcium montanate. Other montanic add esters that may be employed include Licowax E, Licowax OP, and Licolub WE 4 (all from Clariant), for instance, are montanic esters obtained as secondary products from the oxidative refining of raw montan wax. Licowax E and LicolubWE 4 contain montanic adds esterified with ethylene glycol or glycerine. Still other suitable montan wax derivatives may be described in U.S. Pat. No. 5,096,951, as well as in U.S. Patent Application Publication Nos. 2007/0073007; 2006/0100330; and 2004/0254280, all of which are incorporated herein in theft entirety by reference thereto for all purposes.

[0078] Other known waxes may also be employed in a lubricant. Amide waxes, for instance, may be employed that are formed by reaction of a fatty acid with a monoamine or diamine (e.g., ethylenediamine) having 2 to 18, especially 2 to 8, carbon atoms. For example, ethylenebisamide wax, which is formed by the amidization reaction of ethylene diamine and a fatty acid, may be employed. The fatty acid may be in the range from C.sub.12 to C.sub.30, such as from stearic acid (C.sub.18 fatty acid) to form ethylenebisstearamide wax. Ethylenebisstearamide wax is commercially available from Lonza Inc. under the designation Acrawax C, which has a discrete melt temperature of 142 C. Other ethylenebisamides include the bisamides formed from lauric acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, oleostearic acid, myristic acid and undecalinic acid. Still other suitable amide waxes are N-(2-hydroxyethyl)12-hydroxystearamide and N,N-(ethylerie bis)12-hydroxystearamide, which are commercially available from CasChem, a division of Rutherford Chemicals LLC, under the designations Paricin 220 and Paricin 285, respectively.

[0079] In one embodiment, the carbon fiber reinforced polymer composition comprises a polybutylene terephthalate polyester, a fatty acid ester, a nucleant, a heat stabilizing agent, and an antioxidant in addition to fibers having a mean fiber length of from about 10 microns to about 1,000 microns. The polybutylene terephthalate may be present in the composition in an amount from about 35% to about 90% by weight. The composition optionally includes a second polyester having a lower crystallinity than the polybutylene terephthalate. In a particularly preferred embodiment, the second, less crystalline polyester is polyethylene terephthalate.

[0080] In addition to the above components, the polymer composition may include various other ingredients. Colorants that may be used include any desired inorganic pigments, such as titanium dioxide, ultramarine blue, cobalt blue, and other organic pigments and dyes, such as phthalocyanines, anthraquinones, and the like. Other colorants include carbon black or various other polymer-soluble dyes. The colorants can generally be present in the composition in an amount up to about 2 percent by weight.

[0081] The present disclosure may be better understood with reference to the following examples.

EXAMPLES

[0082] Various polymer compositions were formulated in accordance with the present disclosure and tested for various properties. The amount of recycled carbon fiber added to the compositions varied. The following results were obtained.

TABLE-US-00001 TABLE 1 10% Recycled CF Sample No. Norm Formulation ISO Unit 1 2 3 4 5 6 Polybutylene % 86 86 85.5 85.5 71 71 Terephthalate MVR38 Montanic acid triol ester % 0.25 0.25 0.25 0.25 0.25 0.25 nucleant (Talcum) % 0.15 0.15 0.15 0.15 0.15 0.15 Pentaerythritol tetrakis(3- % 0.08 0.08 0.08 0.08 0.08 0.08 (3,5-di-tert-butyl-4- hydroxyphenyl)propionate) Bis-(2,4-di-t-butylphenol) % 0.17 0.17 0.17 0.17 0.17 0.17 Pentaerythritol Diphosphite Titanate coupling agent % 0 0 0.3 0.3 0 0 Polyethylene 0 0 0 0 15 15 terephthalate Intrinsic Viscosity 0.77 Polybutylene % 0.35 0.35 0.55 0.55 0.35 0.35 Terephthalate grind Polybutylene Terephthalate % 2 0 2 0 2 0 95076 black Masterbatch Polyethylene 950231 % 0 2 0 2 0 2 black masterbatch recycled carbon fiber r-CF % 11 11 11 11 11 11 Total % 100 100 100 100 100 100 ash* 1172 % 12.09 12.42 12.69 11.77 12.27 14.55 MVR 250 C./2, 16 kg 1133 cm.sup.3/10 22 21.6 27.2 min Tensile Modulus 527-1/2 MPa 8,896 7,540 8,759 7,757 9062 8420 Tensile Strength 527-1/2 MPa 118 98 116 98.3 118 104.6 Elongation @ Break 527-1/2 % 3.6 4.4 3 3.5 3.3 4.5 Charpy Impact 179/1eU kJ/m.sup.2 33 42.2 29 41.1 29 39.5 Strength @ 23 C. Density g/cm.sup.3 1.353 1.361 Spec. IEC Ohm 8.E+11 4.E+11 Surface Resistivity 60093 8.E+11 5.E+11 4.E+11 5.E+11 Spec. IEC Ohm .Math. m 2.E+04 2.E+04 Volume Resistivity 60093 9.E+04 1.E+04 9.E+04 1.E+04

TABLE-US-00002 TABLE 2 15% Recycled CF Sample No. Formulation Norm ISO Unit 7 8 9 10 Polybutylene Terephthalate % 80.5 80.5 65.5 65.5 MVR38 Montanic acid triol ester % 0.25 0.25 0.25 0.25 nucleant (Talcum) % 0.15 0.15 0.15 0.15 Pentaerythritol tetrakis(3- % 0.08 0.08 0.08 0.08 (3,5-di-tert-butyl-4- hydroxyphenyl)propionate) Bis-(2,4-di-t-butylphenol) % 0.17 0.17 0.17 0.17 Pentaerythritol Diphosphite Titanate coupling agent % 0 0 0 0 Polyethylene terephthalate 0 0 15 15 Intrinsic Viscosity 0.77 Polybutylene Terephthalate % 0.35 0.35 0.35 0.35 grind Polybutylene Terephthalate % 2 0 2 0 95076 black masterbatch Polyethylene 950231 black % 0 2 0 2 masterbatch recycled carbon fiber r-CF % 16.5 16.5 16.5 16.5 Total % 100 100 100 100 ash* 1172 % 15.96 18.52 17.97 19.73 MVR 250 C./2, 16 kg 1133 cm.sup.3/10 min 18.6 21.5 Tensile Modulus 527-1/2 MPa 12,462 11,271 13110 12073 Tensile Strength 527-1/2 MPa 139 121.4 142 125 Elongation @ Break 527-1/2 % 3.1 3.5 3 3.7 Charpy Impact 179/1eU kJ/m.sup.2 47 46.3 47.9 51.1 Strength @ 23 C. Density g/cm.sup.3 1.372 1.376 Spec. IEC 60093 Ohm 8.E+03 4.E+04 Surface Resistivity IEC 60093 Ohm 6.E+03 6.E+04 IEC 60093 Ohm 7.E+03 1.E+05 Spec. IEC 60093 Ohm .Math. m 4.E+01 2.E+02 Volume Resistivity IEC 60093 Ohm.m 4.E+01 2.E+02 IEC 60093 Ohm .Math. m 4.E+01 2.E+02

TABLE-US-00003 TABLE 3 20% Recycled CF Sample No. Norm Formulation ISO Unit 11 12 13 14 15 16 Polybutylene % 75 75 75 55 55 55 Terephthalate MVR38 Montanic acid triol ester % 0.25 0.25 0.25 0.25 0.25 0.25 nucleant (Talcum) % 0.15 0.15 0.15 0.15 0.15 0.15 Pentaerythritol tetrakis(3- % 0.08 0.08 0.08 0.08 0.08 0.08 (3,5-di-tert-butyl-4- hydroxyphenyl)propionate) Bis-(2,4-di-t-butylphenol % 0.17 0.17 0.17 0.17 0.17 0.17 Pentaerythritol Diphosphite Polyethylene % 0 0 0 20 20 20 terephthalate Intrinsic Viscosity 0.77 Polybutylene % 0.35 0.35 0.35 0.35 0.35 0.35 Terephthalate grind Polybutylene Terephthalate % 2 0 0 2 0 0 95076 black masterbatch Polyethylene 950231 % 0 2 2 0 2 2 black masterbatch recycled carbon fiber r-CF % 22 22 22 22 22 22 Total % 100 100 100 100 100 100 ash* 1172 % 22.48 22.87 23.4 23.6 23.94 25.12 MVR 250 C./2, 16 kg 1133 cm.sup.3/10 min 14.7 17.1 Tensile Modulus 527-1/2 MPa 16,730 14,806 15,992 17,145 14,972 16,930 Tensile Strength 527-1/2 MPa 158 140.3 156 163 142.3 160 Elongation @ Break 527-1/2 % 2.3 2.6 2.8 2.5 3 2.8 Charpy Impact 179/1eU kJ/m.sup.2 48 48.3 52 51 53.4 53 Strength @ 23 C. Density g/cm.sup.3 1.393 1.400 1.405 1.400 Spec. IEC Ohm 4.E+01 1.E+03 Surface Resistivity 60093 4.E+01 1.E+03 4.E+01 1.E+03 Spec. IEC Ohm .Math. m 3.E+00 6.E+00 Volume Resistivity 60093 3.E+00 6.E+00 3.E+00 7.E+00

TABLE-US-00004 TABLE 4 30% Recycled CF Sample No. Norm Formulation ISO Unit 17 18 19 20 20 22 Polybutylene % 64 64 64 39 39 39 Terephthalate MVR38 Montanic acid triol ester % 0.25 0.25 0.25 0.25 0.25 0.25 nucleant (Talcum) % 0.15 0.15 0.15 0.15 0.15 0.15 Pentaerythritol tetrakis(3- % 0.08 0.08 0.08 0.08 0.08 0.08 (3,5-di-tert-butyl-4- hvdroxyphenyl)propionate) Bis-(2,4-di-t-butylphenol) % 0.17 0.17 0.17 0.17 0.17 0.17 Pentaerythritol Diphosphite Polyethylene % 0 0 0 25 25 25 terephthalate Intrinsic Viscosity 0.77 Polybutylene % 0.35 0.35 0.35 0.35 0.35 0.35 Terephthalate grind Polybutylene % 2 0 0 2 0 0 Terephthalate 95076 black masterbatch Polyethylene 950231 % 0 2 2 0 2 2 black masterbatch recycled CF % 33 33 33 33 33 33 Total % 100 100 100 100 100 100 ash* 1172 % 32.52 34.11 33.73 34.26 34.98 35.3 MVR 250 C./2, 16 kg 1133 cm.sup.3/10 min 9.7 10.4 Tensile Modulus 527-1/2 MPa 24,272 22,679 23,338 25,400 23,345 24,718 Tensile Strength 527-1/2 MPa 180 164.2 180 191 173.7 186 Elongation @ Break 527-1/2 % 1.5 1.5 1.9 1.7 1.8 1.8 Charpy Impact 179/1eU kJ/m.sup.2 49 47.9 55 54.4 55 57 Strength @ 23 C. Density g/cm.sup.3 1.432 1.440 1.452 1.440 Spec. IEC Ohm 4.E+01 6.E+01 Surface Resistivity 60093 4.E+01 6.E+01 4.E+01 7.E+01 Spec. IEC Ohm .Math. m 4.E01 8.E01 Volume Resistivity 60093 5.E01 8.E01 4.E01 8.E01

TABLE-US-00005 TABLE 5 40% Recycled CF Sample No. Norm Formulation ISO Unit 23 24 25 26 27 28 Polybutylene Terephthalate % 53 53 53 23 23 23 MVR38 Montanic acid triol ester % 0.25 0.25 0.25 025 0.25 0.25 nucleant (Talcum) % 0.15 0.15 0.15 0.15 0.15 0.15 Pentaerythritol tetrakis(3- % 0.08 0.08 0.08 0.08 0.08 0.08 (3,5-di-tert-buty1-4- hydroxyphenyl)propionate) Bis-(2, 4-di-t-butylphenol) % 0.17 0.17 0.17 0.17 0.17 0.17 Pentaerythritol Diphosphite Polyethylene terephthalate % 0 0 0 30 30 30 Intrinsic Viscosity 0.77 Polybutylene Terephthalate % 0.35 0.35 0.35 0.35 0.35 0.35 grind Polybutylene Terephthalate % 2 0 0 2 0 0 95076 black masterbatch Polyethylene 950231 black % 0 2 2 0 2 2 masterbatch recycled carbon fiber r-CF % 44 44 44 44 44 44 Total % 100 100 100 100 100 100 ash* 1172 % 43.75 43.55 43.86 45.6 45.06 45.09 MVR 250 C./2, 16 kg 1133 cm.sup.3/10 5.4 6.9 min Tensile Modulus 527-1/2 MPa 31,596 29,669 31,787 33,937 32,039 32,371 Tensile Strength 527-1/2 MPa 182 171.2 189 204 187.2 191 Elongation @ Break 527-1/2 % 1 1 1.1 1 1.1 1.1 Charpy Impact Strength @ 179/1eU kJ/m.sup.2 43 43.6 55 49 48.3 52 23 C. Density g/cm.sup.3 1.481 1.480 1.503 1.480 Spec. IEC Ohm 2.E+01 3.E+01 Surface Resistivity 60093 2.E+01 3.E+01 2.E+01 3.E+01 Spec. IEC Ohm .Math. 2.E01 3.E01 Volume Resistivity 60093 m 3.E01 4.E01 2.E01 4.E01

[0083] These and other modifications and variations to the present invention may be practiced by those of ordinary skill in the art, without departing from the spirit and scope of the present invention, which is more particularly set forth in the appended claims. In addition, it should be understood that aspects of the various embodiments may be interchanged both in whole or in part. Furthermore, those of ordinary skill in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the invention so further described in such appended claims.