Process for gas phase surface treatment

Patent metadata

Field	Value
Publication number	US-10060053-B2
Application number	US-201615382832-A
Country	US
Kind code	B2
Filing date	Dec 19, 2016
Priority date	Dec 22, 2015
Publication date	Aug 28, 2018
Grant date	Aug 28, 2018

Abstract

A gas phase surface treatment for treating carbon fiber including (a) exposing a carbon fiber to a gaseous oxidizing atmosphere to form a modified carbon fiber with an oxidized fiber surface; followed by (b) exposing the oxidized fiber surface to a gaseous nitrogen-containing atmosphere to form a modified carbon fiber with a nitrogen-enriched surface, wherein the nitrogen-enriched surface exhibits an increase in surface nitrogen to surface carbon (N/C) ratio as compared to the surface of the carbon fiber prior to exposure at (a). Steps (a) and (b) are carried out continuously without any additional intervening surface treatment.

First claim

The invention claimed is:

1. A gas phase surface treatment for treating a continuous carbon fiber, comprising:
a) exposing a moving continuous carbon fiber to a gaseous oxidizing atmosphere to form a modified carbon fiber with an oxidized fiber surface; followed by
b) exposing the moving continuous carbon fiber with the oxidized fiber surface to a gaseous nitrogen-containing atmosphere comprising at least 50% by volume of ammonia gas to form a modified carbon fiber with a nitrogen-enriched surface, wherein the nitrogen-enriched surface exhibits an increase in surface nitrogen to surface carbon (N/C) ratio as compared to the surface of the carbon fiber prior to exposure at (a),
wherein steps (a) and (b) are carried out continuously without any additional intervening surface treatment,
wherein step (a) is carried out for a period of 0.5-2 minutes, and step (b) is carried out for a period of 0.5-2 minutes.

2. The gas phase surface treatment of claim 1 wherein, the increase in N/C ratio is at least 30% as measured by X-ray photoelectron spectroscopy (XPS).

3. The gas phase surface treatment of claim 1 wherein, the N/C ratio of the nitrogen-enriched surface is in the range of 0.05-0.07 as measured by X-ray photoelectron spectroscopy (XPS).

4. The gas phase surface treatment according to claim 1 , wherein steps (a) and (b) are performed immediately, without any intervening step, after carbonization of a stabilized polyacrylonitrile (PAN) fiber precursor to produce said carbon fiber.

5. The gas phase surface treatment according to claim 1 , wherein the gaseous oxidizing atmosphere comprises ozone and at least one gaseous component selected from: air, oxygen, nitrogen oxide, and combination thereof.

6. The gas phase surface treatment according to claim 1 , wherein the gaseous oxidizing atmosphere comprises at least 1000 ppm of ozone.

7. The gas phase surface treatment according to claim 1 , wherein steps (a) and (b) are performed at a temperature in the range of about 100° C. to about 200° C.

8. The gas phase surface treatment of claim 7 , wherein steps (a) and (b) are performed at a temperature in the range of 120° C. to 160° C.

9. A continuous process for manufacturing carbon fiber comprising:
i. passing a continuous polyacrylonitrile (PAN) fiber through an oxidation zone to form a stabilized PAN fiber;
ii. passing the stabilized PAN fiber through a carbonization zone to form a continuous carbon fiber;
iii. exposing the continuous carbon fiber to a gaseous oxidizing atmosphere to form a modified carbon fiber with an oxidized fiber surface; and
iv. exposing the oxidized fiber surface to a gaseous nitrogen-containing atmosphere comprising at least 50% by volume of ammonia gas to form a modified carbon fiber with a nitrogen-enriched surface, wherein the nitrogen-enriched surface exhibits an increase in surface nitrogen to surface carbon (N/C) ratio as compared to the surface of the carbon fiber prior to exposure at (iii),
wherein steps (i) to (iv) or steps (ii) to (iv) are carried out continuously,
wherein step (iii) is carried out for a period of 0.5-2 minutes, and step (iv) is carried out for a period of 0.5-2 minutes.

10. The continuous process of claim 9 , wherein N/C ratio of the nitrogen-enriched surface is in the range of 0.05-0.07 as measured by X-ray photoelectron spectroscopy (XPS).

11. The continuous process of claim 9 , wherein the increase in N/C ratio is at least 30%.

12. The continuous process according to claim 9 , wherein the gaseous oxidizing atmosphere comprises ozone and at least one gaseous component selected from: air, oxygen, nitrogen oxide, and combination thereof.

13. The continuous process according to claim 9 , wherein the gaseous oxidizing atmosphere comprises at least 1000 ppm of ozone.

14. The continuous process according to claim 9 , wherein the oxidation zone at (i) comprises an oven configured to enclose the continuous PAN fiber in air.

15. The continuous process of claim 14 , wherein the oven of the oxidation zone is maintained at a temperature in the range of 200° C.-300° C.

16. The continuous process according to claim 9 , wherein the carbonization zone at (ii) comprises one or more furnace(s), each enclosing a gaseous atmosphere comprising at least 99% by volume of an inert gas.

17. The continuous process of claim 16 , wherein the one or more furnace(s) of the carbonization zone is/are maintained at a temperature in the range of 300° C.-1650° C.

18. The continuous process of claim 16 , wherein the carbonization zone at (ii) comprises a pre-carbonization furnace maintained at a lower temperature in the range of 300° C.-900° C. and a carbonization furnace maintained at a higher temperature in the range of 700° C.-1650° C.

Assignees

• Cytec Ind Inc

Inventors

• Chiu Shao C

Classifications

• D06M2101/40

  Fibres of carbon · CPC title

• D01F11/128 Primary

  Nitrides, nitrogen carbides (nitrogen borides D01F11/124) · CPC title

• D01F11/122

  Oxygen, oxygen-generating compounds (anode oxidising D01F11/16) · CPC title

• D01F9/22 Primary

  from polyacrylonitriles · CPC title

• C08J5/06

  using pretreated fibrous materials · CPC title