IP Library Granted Patent US 9,783,454
Granted Patent B2
US 9,783,454 · App. 12/976,261 · Granted Oct 10, 2017

High strength glass composition and fibers

Inventors: Robert L. Hausrath (Aiken, SC); Anthony V. Longobardo (Johnston, SC)
Assignee: AGY Holding Corp.
C03C13/00C03C3/087C08J5/08C08J5/24C08J2300/24C08J2363/00
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Quick Facts
Patent No.
US 9,783,454
App. No.
12/976,261
Granted
Oct 10, 2017
Kind
B2
Abstract

Glass compositions and high-modulus, and high-strength glass fibers made therefrom, being capable of economical, continuous processing and suitable for the production of high-strength and/or high stiffness, low-weight composites, such as windturbine blades, the glass composition comprises the following constituents in the limits defined below, expressed as weight percentages: between about 56 to about 61 weight percent SiO 2 ; between about 16 to about 23 weight percent Al 2 O 3 , wherein the weight percent ratio of SiO 2 /Al 2 O 3 is between about 2 to about 4; between about 8 to about 12 weight percent MgO; between about 6 to about 10 weight percent CaO, wherein the weight percent ratio of MgO/CaO is between about 0.7 to about 1.5; between about 0 to about 2 weight percent Na 2 O; less than about 1 weight percent Li 2 O; and total residual transition metal oxides of less than about 2 weight percent.

Claims (72)

1. A glass composition comprising:

between 56 to 59.87 weight percent SiO 2 ;

between 20.97 to 23 weight percent Al 2 O 3 , wherein the weight percent ratio of SiO 2 /Al 2 O 3 is between 2 to 4;

between 8 to 12 weight percent MgO;

between 6 to 10 weight percent CaO; wherein the weight percent ratio of MgO/CaO is between 0.7 to 1.5;

between 0 to 2 weight percent Na 2 O;

less than 1 weight percent TiO 2 ;

less than 1 weight percent B 2 O 3 ;

essentially free of intentionally added Li 2 O; and

total residual transition metal oxides of less than 2 weight percent.

2. The glass composition of claim 1 , wherein the glass composition is less than 0.25 weight percent unintentionally added Li 2 O.

3. The glass composition of claim 1 , wherein the glass composition is essentially potassium free.

4. The glass composition of claim 1 , wherein the glass composition is essentially lithium free and potassium free.

5. The glass composition of claim 1 , wherein the glass composition has a liquidus temperature of between 1240° C. and 1270° C. and a T 2 of less than 1550° C.

6. A glass fiber comprising:

between 56 to 59.87 weight percent SiO 2 ;

between 20.97 to 23 weight percent Al 2 O 3 , wherein the weight percent ratio of SiO 2 /Al 2 O 3 is between 2 to 4;

between 8 to 12 weight percent MgO;

between 6 to 10 weight percent CaO, wherein the weight percent ratio of MgO/CaO is between 0.7 to 1.5;

between 0 to 2 weight percent Na 2 O;

less than 1 weight percent TiO 2 ;

less than 1 weight percent B 2 O 3 ;

essentially free of intentionally added Li 2 O; and

total residual transition metal oxides of less than 2 weight percent.

7. The glass fiber of claim 6 , wherein the glass fiber is essentially potassium free.

8. The glass fiber of claim 6 , wherein the glass fiber is less than 0.25 weight percent unintentionally added Li 2 O and potassium free.

9. The glass fiber of claim 6 , wherein the glass fiber has a pristine fiber strength of at least 4400 MPa.

10. The glass fiber of claim 6 , wherein the glass fiber has a Young's modulus of at least 90 GPa.

11. The glass fiber of claim 6 , consisting essentially of:

between 56 to 59.87 weight percent SiO 2 ;

between 20.97 to 23 weight percent Al 2 O 3 , wherein the weight percent ratio of SiO 2 /Al 2 O 3 is between 2 to 4;

between 8 to 12 weight percent MgO;

between 6 to 10 weight percent CaO, wherein the weight percent ratio of MgO/CaO is between 0.7 to 1.5;

between 0 to 2 weight percent Na 2 O;

less than 1 weight percent TiO 2 ;

less than 1 weight percent B 2 O 3 ;

essentially free of intentionally added Li 2 O; and

total residual transition metal oxides of less than 2 weight percent.

12. A process for providing continuous, manufacturable, high modulus glass fibers in a glass melter, the process comprising the steps of:

providing a composition to a melting zone of a glass melter, the composition comprising:

between 56 to 59.87 weight percent SiO 2 ;

between 20.97 to 23 weight percent Al 2 O 3 , wherein the weight percent ratio of SiO 2 /Al 2 O 3 is between 2 to 4;

between 8 to 12 weight percent MgO;

between 6 to 10 weight percent CaO; wherein the weight percent ratio of MgO/CaO is between 0.7 to 1.5;

between 0 to 2 weight percent Na 2 O;

less than 1 weight percent TiO 2 ;

less than 1 weight percent B 2 O 3 ;

less than 0.25 weight percent unintentionally added Li 2 O; and

total residual transition metal oxides of less than 2 weight percent;

heating the composition to a forming temperature in excess of the liquidus temperature of a resulting glass to form a fiberizable molten glass; and

continuously fiberizing said molten glass wherein a manufacturable high modulus glass fiberization process is sustained.

13. The process of claim 12 , wherein the composition comprises between 56 to 59.87 weight percent SiO 2 ; between 20.97 to 23 weight percent Al 2 O 3 , wherein the weight percent ratio of SiO 2 /Al 2 O 3 is between 2 to 4; between 8 to 12 weight percent MgO; between 6 to 10 weight percent CaO, wherein the weight percent ratio of MgO/CaO is between 0.7 to 1.5; between 0 to 2 weight percent Na 2 O; less than 1 weight percent TiO 2 ; less than 1 weight percent B 2 O 3 ; less than 0.25 weight percent unintentionally added Li 2 O; and total residual transition metal oxides of less than 2 weight percent.

14. The process of claim 12 , wherein the composition has a fiberizing temperature of less than 1375° C., and a delta-T (ΔT) of at least 70° C.

15. The process of claim 12 , wherein the glass fiber produced from said composition has a pristine fiber strength of at least 4400 MPa.

16. The process of claim 12 , further comprising impregnating the glass fiber produced from said composition, wherein the glass fiber has an impregnated strand tensile modulus of greater than 85 GPa.

17. The process of claim 12 , further comprising impregnating the glass fiber produced from said composition, wherein the glass fiber has an impregnated strand tensile modulus of 90 GPa.

18. A fiberglass reinforced article comprising:

glass fibers comprising:

between 56 to 59.87 weight percent SiO 2 ;

between 20.97 to 23 weight percent Al 2 O 3 , wherein the weight percent ratio of SiO 2 /Al 2 O 3 is between 2 to 4;

between 8 to 12 weight percent MgO;

between 6 to 10 weight percent CaO, wherein the weight percent ratio of MgO/CaO is between 0.7 to 1.5;

between 0 to 2 weight percent Na 2 O;

less than 1 weight percent TiO 2 ;

less than 1 weight percent B 2 O 3 ;

essentially free of intentionally added Li 2 O; and

total residual transition metal oxides of less than 2 weight percent; and

a matrix material.

19. The fiberglass reinforced article of claim 18 , wherein the glass fibers comprise between 56 to 59.87 weight percent SiO 2 ; between 20.97 to 23 weight percent Al 2 O 3 , wherein the weight percent ratio of SiO 2 /Al 2 O 3 is between 2 to 4; between 8 to 12 weight percent MgO; between 6 to 10 weight percent CaO, wherein the weight percent ratio of MgO/CaO is between 0.7 to 1.5; between 0 to 2 weight percent Na 2 O; less than 1 weight percent TiO 2 ; less than 1 weight percent B 2 O 3 ; less than 0.25 weight percent unintentionally added Li 2 O; and total residual transition metal oxides of less than 2 weight percent.

20. The fiberglass reinforced article of claim 18 , wherein said fiberglass reinforced article is a wind turbine blade.

21. The fiberglass reinforced article of claim 18 , wherein the glass fibers of the fiberglass reinforced article have an impregnated strand tensile modulus of greater than 85 GPa.

22. The fiberglass reinforced article of claim 18 , wherein the glass fibers of the fiberglass reinforced article have an impregnated strand tensile modulus of 90 GPa.

Assignments (14)
RELEASE OF SECURITY INTEREST Recorded Sep 21, 2020
From: WELLS FARGO BANK, NATIONAL ASSOCIATION
To: AGY HOLDING CORP.
Reel/Frame 053836/0520 →
RELEASE OF SECURITY INTEREST Recorded Sep 21, 2020
From: U.S. BANK NATIONAL ASSOCIATION
To: AGY HOLDING CORP.
Reel/Frame 053836/0470 →
SECURITY INTEREST Recorded Sep 21, 2020
From: AGY HOLDING CORP.
To: TCW ASSET MANAGEMENT COMPANY LLC
Reel/Frame 053836/0429 →
PATENT SECURITY AGREEMENT Recorded Jul 24, 2015
From: AGY HOLDING CORP.
To: WELLS FARGO BANK, NATIONAL ASSOCIATION
Reel/Frame 036180/0047 →
CORRECTIVE ASSIGNMENT TO CORRECT THE ASSIGNEES' AND ASSIGNOR'S NAME PREVIOUSLY RECORDED ON REEL 035904 FRAME 0070. ASSIGNOR(S) HEREBY CONFIRMS THE RELEASE OF SECURITY INTEREST IN PATENTS. Recorded Jun 26, 2015
From: UBS AG
To: AGY HOLDING CORP.; AGY AIKEN LLC; AGY PA OPERATIONS LLC F/K/A AGY HUNTINGDON LLC
Reel/Frame 036080/0313 →
RELEASE OF SECURITY INTEREST IN PATENTS Recorded Jun 12, 2015
From: AGY HOLDING CORP.; AGY AIKEN LLC; AGY PA OPERATIONS LLC F/K/A AGY HUNTINGDON LLC
To: UBS AG
Reel/Frame 035904/0070 →
RELEASE OF SECURITY INTEREST Recorded Jun 10, 2015
From: UBS AG, STAMFORD BRANCH, AS AGENT
To: AGY HOLDING CORP.; AGY AIKEN LLC; AGY HUNTINGDON LLC
Reel/Frame 035880/0051 →
PATENT SECURITY AGREEMENT Recorded Jul 1, 2013
From: AGY HOLDING CORP.
To: WELLS FARGO BANK, NATIONAL ASSOCIATION, AS COLLATERAL AGENT
Reel/Frame 030744/0823 →
PATENT SECURITY AGREEMENT Recorded Jul 1, 2013
From: AGY HOLDING CORP.
To: U.S. BANK NATIONAL ASSOCIATION, AS COLLATERAL AGENT
Reel/Frame 030744/0838 →
SECURITY AGREEMENT Recorded May 13, 2013
From: AGY HOLDING CORP.; AGY AIKEN LLC; AGY HUNTINGDON LLC
To: UBS AG, STAMFORD BRANCH, AS AGENT
Reel/Frame 030406/0847 →
RELEASE OF SECURITY INTEREST Recorded May 13, 2013
From: BANK OF AMERICA, N.A., AS AGENT
To: AGY HOLDING CORP.; AGY AIKEN LLC; AGY HUNTINGDON LLC
Reel/Frame 030405/0327 →
SECURITY AGREEMENT Recorded Mar 9, 2011
From: AGY HOLDING CORP.
To: BANK OF AMERICA, N.A.
Reel/Frame 025920/0217 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 22, 2010
From: HAUSRATH, ROBERT L.; LONGOBARDO, ANTHONY V.
To: AGY HOLDING CORPORATION
Reel/Frame 025765/0340 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 22, 2010
From: HAUSRATH, ROBERT L.; LONGOBARDO, ANTHONY V.
To: AGY HOLDING CORPORATION
Reel/Frame 025721/0776 →
Continuity (1)
Related Publication 20120163987A1 · Jun 28, 2012