High throughput carbon fiber surface modification

Patent metadata

Field	Value
Publication number	US-12435465-B2
Application number	US-202017429860-A
Country	US
Kind code	B2
Filing date	Feb 11, 2020
Priority date	Feb 12, 2019
Publication date	Oct 7, 2025
Grant date	Oct 7, 2025

Abstract

Typical commercial surface treatments for continuous carbon fibers are often unavailable for discontinuous fibers. As such, there is little variety of chopped fiber surfaces leading to non-ideal coating solutions which result in poor interfacial compatibility between fibers and a composite matrix. A method of applying a highly effective coating using a high throughput technique for chopped carbon fibers. The method provides the ability to tune both the coating thickness and chemical functionality using processing parameters. The coatings are evaluated using X-ray photoelectron spectroscopy (XPS) for uniformity and composition. Using this technique, thermoplastic composites are highlighted showing an increase in interfacial shear strength (IFSS) of 25 MPa. This process shows promise for increasing the throughput of surface treatment of chopped fiber on the industrial scale.

First claim

What is claimed is:

1. A method of modifying a surface of carbon fiber having a functional moiety, said method comprising steps of:
(a) contacting in a reactor, in the absence of a solvent, the surface of the carbon fiber with a vapor phase of a silane capable of covalent bonding to the functional moiety on the surface of the carbon fiber or depositing via condensation on the surface of the carbon fiber; wherein said contacting step is conducted in a sealed container under a vacuum pressure ranging from the vapor pressure of the silane to up to about 101325 Pa for a sufficient time to covalently bond at least some of said silane to the functional moiety on the surface of the carbon fiber; and
(b) exposing the carbon fiber produced in step (a) to a temperature of from about 25° C. to about 200° C. for a period of from about 1 minute to about 96 hours to crosslink at least some of the silane on the surface of the carbon fiber; wherein
i) the carbon fiber and the reactor each have a volume and a ratio of the volume of the carbon fiber to the reactor volume is from about 0.1 to about 0.6, the contacting step is carried out at a pH of from about 5 to about 7 and the temperature of the exposing step is from about 75° C. to about 125° C., or
ii) further comprising a step of condensing the vapor phase at the end of the contacting step and prior to the exposing step by equilibrating the vapor phase and the carbon fiber to a pressure above the vapor pressure of the silane to condense at least some liquid silane onto the surface of the carbon fiber and said exposing step crosslinks at least some of the silane groups covalently bound to the surface of the carbon fibers and at least some of the liquid silane condensed onto the surface of the carbon fiber.

2. The method of claim 1 , wherein the functional moiety on the surface of the carbon fiber comprises one or more hydroxyl groups, one or more carboxyl groups, a combination of hydroxyl groups and carboxyl groups or a combination of hydroxyl groups, carboxyl groups and amine groups.

3. The method of claim 1 , wherein the functional moiety on the surface of the carbon fiber is formed by one or more of the following methods, ozone treatment, plasma, treatment with an acid, hydride chemistry, treatment with a base, thermal oxidation, and gamma radiation.

4. The method of claim 1 , wherein the carbon fiber has an average length of from about 1 mm to about 100 mm and an average fiber diameter of from about 1 μm to about 100 μm.

5. The method of claim 1 , wherein the carbon fiber is chopped carbon fiber.

6. The method of claim 1 , wherein the silane is an organosilane or a functionalized organosilane selected from the group consisting of acrylate and methacrylate functional silanes, aldehyde functional silanes, amino functional silanes, anhydride functional silanes, azide functional silanes, carboxylate functional silanes, phosphonate functional silanes, sulfonate functional silanes, epoxy functional silanes, ester functional silanes, halogen functional silanes, hydroxyl functional silanes, isocyanate and masked isocyanate functional silanes, phosphine and phosphate functional silanes, sulfur functional silanes, vinyl and olefin functional silanes, multi-functional and polymeric silanes, UV active and fluorescent silanes, chiral silanes, trihydrosilanes, and dipodal silanes.

7. The method of claim 1 , wherein the silane is selected from the group consisting of (3-aminopropyl) trimethoxysilane, (3-aminopropyl) triethoxysilane, (3-acryloxypropyl) trimethoxysilane, (3-triethoxysilyl) propyl succinic anhydride, and ((chloromethyl) phenylethyl) trimethoxy silane.

8. The method of claim 1 , wherein surface modification of the surface of the carbon fiber is controlled by controlling at least two of the following parameters, process temperature, vacuum pressure, humidity, exposure time, fiber/reactor volume ratio, pH, and crosslinking temperature.

9. The method of claim 1 , wherein the vacuum pressure is from about 10 −3 mmHg to about 200 mmHg.

10. The method of claim 1 , wherein the contacting step is carried out at a temperature of from about 0° C. to about 200° C.

11. The method of claim 1 , wherein the contacting step is carried out at a relative humidity of from about 0% to about 10% for an exposure time of from 30 minutes to 60 minutes.

12. The method of claim 1 , wherein the ratio of the volume of the carbon fiber to the reactor volume is from about 0.1 to about 0.6, the contacting step is carried out at the pH of from about 5 to about 7 and the temperature of the exposing step is from about 75° C. to about 125° C.

13. The method of claim 1 , comprising the step of condensing the vapor phase at the end of the contacting step and prior to the exposing step by equilibrating the vapor phase and the carbon fiber to the pressure above the vapor pressure of the silane to condense at least some liquid silane onto the surface of the carbon fiber and said exposing step crosslinks at least some of the silane groups covalently bound to the surface of the carbon fibers and at least some of the liquid silane condensed onto the surface of the carbon fiber.

14. The method of claim 1 , wherein a sufficient amount of silane is present in the contacting step to provide a saturated vapor phase.

15. The method of claim 1 , wherein the amount of silane deposited is controlled by carrying out the contacting step with a vapor phase that is less than saturated.

Assignees

• Univ Drexel

Inventors

• Hinton Zachary R
• Alvarez Nicolas Javier
• Palmese Giuseppe Raffaello

Classifications

• D06M2101/40

  Fibres of carbon · CPC title

• D06M23/06

  Processes in which the treating agent is dispersed in a gas, e.g. aerosols (aerosol compositions C09K3/30) · CPC title

• D06M15/643 Primary

  containing silicon in the main chain · CPC title

• D06M10/04 Primary

  Physical treatment combined with treatment with chemical compounds or elements (graft polymerisation using wave energy or particle radiation D06M14/18 {; treatment with radioactive elements D06M10/008}) · CPC title