High modules crosslinked polyethylene with reduced residual free radical concentration prepared below the melt

1. A method of decreasing residual free radical concentration in an irradiated crosslinked polyethylene composition, wherein the method comprises the steps of:

a) irradiating polyethylene at a temperature that is below the melting point of the polyethylene;

b) mechanically deforming the polyethylene from step a) at a temperature that is above room temperature and below the melting point of the irradiated polyethylene in order to decrease the concentration of residual free radicals; and

(c) allowing the polyethylene from step b) to cool following the deformation.

2. The method of claim 1 , wherein the mechanical deforming is by pressure, and wherein the deforming temperature is less than about 140° C.

3. The method of claim 1 , wherein the polyethylene is irradiated at a dose level between about 1 and about 1,000 kGy.

4. The method of claim 1 , wherein the crosslinked polyethylene has substantially no trapped residual free radical detectable by electron spin resonance.

5. The method of claim 1 , wherein the mechanical deformation mode is selected from the group consisting of channel flow, uniaxial compression, biaxial compression, oscillatory compression, uniaxial tension, biaxial tension, ultra-sonic oscillation, bending, plane stress compression (channel die), and combinations thereof.

6. A method of making an irradiated cross-linked polyethylene composition comprising the steps of:

a) irradiating the polyethylene in an inert environment at a temperature that is above room temperature and below the melting point of the polyethylene; and

b) contacting the polyethylene with a sensitizing environment, thereby reducing concentration of the residual free radicals.

7. The method of claim 6 , wherein the polyethylene is ultra-high molecular weight polyethylene (UHMWPE).

8. The method of claim 6 , wherein the radiation dose level is between about 1 and about 1,000 kGy.

9. The method of claim 6 , wherein the sensitizing environment comprises about 5% by volume acetylene and about 95% by volume nitrogen.

10. The method of claim 6 , wherein the sensitizing environment comprises acetylene.

11. A method of improving oxidation resistance of an irradiated cross-linked polyethylene composition comprising the steps of:

a) irradiating the polyethylene at a temperature that is below the melting point of the polyethylene;

b) mechanically deforming the polyethylene below the melting point of the irradiated polyethylene, thereby reducing concentration of the residual free radicals, and

c) annealing the mechanically deformed polyethylene at a temperature below the polyethylene melting point in order to permit shape recovery.

12. The method of claim 11 , wherein the annealing is carried out in the presence of sensitizing environment.

13. A method of improving oxidation resistance of an irradiated cross-linked polyethylene composition comprising the steps of:

a) irradiating the polyethylene at a temperature that is below the melting point of the polyethylene;

b) mechanically deforming the polyethylene below the melting point of the irradiated polyethylene, thereby reducing concentration of the residual free radicals, and

c) annealing the mechanically deformed polyethylene at a temperature below the polyethylene melting point in order to permit shape recovery, wherein the annealing in the presence of sensitizing environment is carried out at above an ambient atmospheric pressure.

14. The method of claim 13 , wherein the annealing in the presence of sensitizing environment is carried out at above an ambient atmospheric pressure of at least about 1.0 atm.

15. The method of claim 12 , wherein the annealing in the presence of sensitizing environment is carried with high frequency sonication.

16. A method of improving creep resistance of an irradiated cross-linked polyethylene composition comprising the steps of:

a) contacting the polyethylene composition with a sensitizing environment;

b) irradiating by gamma or electron beam radiation; and

c) subjecting the composition to a temperature that is below the melting point of the polyethylene composition while in the presence of a sensitizing environment, thereby improving creep resistance of the polyethylene.

17. The method of claim 16 , wherein the sensitizing environment comprises a diene or a mixture of different dienes.

18. The method of claim 16 , wherein the environment is a mixture of acetylene and nitrogen.

19. The method of claim 16 , wherein the polyethylene composition is further mechanical deformed by ultra-sonic oscillation.

20. The method of claim 19 , wherein the mechanical deformation is performed at an elevated temperature that is below the melting point of the polyethylene.

21. A method of maintaining crystallinity of an irradiated cross-linked polyethylene composition comprising the steps of:

a) mechanically deforming the polyethylene at a solid- or a molten-state;

b) crystallizing the polyethylene at the deformed state at a temperature below the melting point of polyethylene;

c) irradiating the polyethylene that is below the melting point of the polyethylene; and

d) heating the irradiated polyethylene to a temperature that is below the melting point, thereby maintaining the crystallinity of the cross-linked polyethylene composition and aid in shape recovery.

22. The method of claim 21 , wherein the polyethylene is ultra-high molecular weight polyethylene (UHMWPE).

23. The method of claim 21 , wherein irradiation is carried out in air or an inert environment.

24. The method of claim 21 , wherein the deforming temperature is less than about 140° C.

25. The method of claim 21 , wherein crystallinity of the cross-linked polyethylene is at least about 51%.