I

Producing Uitrastrong Giass

iHow far pasf ifs surface shiouid we iook to improve tiie strengtht of a piece of giass?
John T. Brown

For perhaps 7000 years, glass, with its basic qualities, has enhanced society despite its one unchanging weaknessbrittleness. The failure of glass to achieve its full theoretical strength was explained almost 100 years ago hy Griffith. Why then does typical container-glass and sheet-glass achieve only 0.5% of its proved maximum strength? Within the past three decades, the ancient historical definition of glass as a material that must he formed at high temperature has changed. It has heen discovered that chemical polymerization of inorganic glass networks near room temperatures followed hy heat treatment to 45OC drives off excessive terminal hydroxyl and organic groups. This allows nearroom-temperature molecular homogenization of the t^lass oxides. The traditional definition of glass also implies that the material be in a contiguous three-dimensional structure. It also requires transparency, which precludes structural faults or discontinuities in structure that would impair transmission of visihle light. If glass is to take its rightful place in our society, it's hrittleness must he overcome. As important as energy improvements are to the success of the glass industry, brittleness and other pressing needs and opportunities must be pursued.

strength. A greater segment ot our intellectual ctimmunity needs to he involved to meet these needs. It is important to capture the interest of the broadest spectrum of talent. Therefore, a worldwide committee of leading authorities in glass is organizing a glass-strength challenge (See sidehar on page 53). A sizable financial award is expected to engage worldwide talent to solve the glass-strength problem and improve the quality of glass throughout the industry. Commercial glasses have a wide range of strenj::th values, and glass fibers are in the high end of rhe range. The strength of the inside surfaces of blown ware are 4-10 times the strength of the outside surfaces. LCD glass that is only 0.6 mm thick has a strength of 45,000 psi. It essentially is formed without contact, until after annealing and cooling, when it is cut and put in protected containers for transport. The theoretical strength of the Si-O hond is calculated to be >2,000,000 psi. Testing hy the National Institute for Science and Technology has shown that strength is not correlated with composition as much as with surface ciindition. Criffith flaws created in manufacturing contribute to enormous decreases in usable strength, ~0.5% of original pristine strength. Under vacuum conditions, the strength of freshly drawn pristine fibers has been measured at 2,000,000 psi.

Progress and Needs

''
(Top) Molecular model of gloss with a plone cut af 5A from the surfoce.

Significant progress has been made during recent decades toward (overcoming brittleness in glass. However, much more needs to be done to reach the theoretical limitations of glass

54

American Ceromic Society Bulletin, Vol. 86, No. 1

Glass-Fiber Strength
Telecommunications fiber is uutstandiriH in strength when compiired with many other commercial glass products. Glass libers used for telecommunicutit)ns have unique characteristics. The core hiank is stripped of water, well helow detectable limits. The core contains no alkalis. The dry core is induction heated, and the fiber is drawn in a dry, thermally conductive atmosphere. The rate of ctxiling is thousands ofdegrees Celsius per second. Polymer ct>atings are applied to the fiber in fractions of a 'Ccoiii.l after it is drawn to diameter. There is no mechanical contact until the glass fiber is douhled in diameter using ptilymer coatings. These characteristics of telecommunications fibers provide clues lo what is needed tor common commercial-glass manulacturing processes. They also provide clues to what is needed IO pR)duce ultrastrong glass. This might be the path to a solulion (or producing glass that approaches its theoretical strength. A Bell Laboratories breakthrough created a glass fiher more ihiin a mile long that withstood pulling forces up to 600,000 l^si, which was stronger than stainless-steel wire ot the same vliameter.^ A rod of synthetic silica was fire polished to remove ^urface defects. It then was boated, using a laser beam, soft enough to be pulled away in hair-thin lengths and immediately coated witb an organic resin to protect the glass surface. This process resembled the concerns for surface flaws and investment in protection of the just-formed surfaces of (-timing's commercial SMF 28 fiber. The standard telecommunication fiher is 250 fjm in diameter but only 125 fjm is glass. rhe balance, or ~75% of the volume, is polymer protection.
1M1 I 1 High values for glass fibers 10G

1
/ Abraded surfaces Glass-ceramk: as mads 1G S a.

J . 100kC

(Blown)

Ctiem-tempered As formed commercial surfaces Thermal-tempefed Annealed

(Pressed)

"^

10k-

Abraded

K'

3>
100M ^

Approx. severely abraded tongterm m Design strength for annealed glass

Normal modulus of rigidity of commercial glasses.

tbe author, "If chemical companies knew as little about the surfaces of tbeir products as glass manufacturers and scientists appear to know about glass surfaces, the chemical companies would he out of husiness."

Glass-Strength Testing
In December 1936, glass rods, 0.25 in. in diameter and 10 in. in length, were drawn at the Steuhen factory from Code 0081 (73.5% SiO,, 1.2% AUO,, 16.8% Na,O, 4.8% MgO and 0.22% K^O) glass. Tbey were acid fortified and lacquer coated for protection and put under 150,000 psi stress. In 1962, one rod was stress relieved and then returned, essentially, to the original shape.

A fledgling telecommunications group instituted a second long-temi test in November 1977. More tban IOO individual t)ptical telecommunications fibers were stress tested and were under load hy January 1978. These were pilot-plant optical waveguide fibers with 6 ^im cellulose acetate single lacquer coating on 125 pni glass fiher. The fibers were all outside vapor deposited (OVD). Pyrex chemical tubes in 6 ft lengths were Surface Conditions used to hold the test fibers and protect tbem from tbe environment. Tbe pipes also beld tbe deionized (Dl) water tbat was hi 1920, Griffith' identified surtace conditions as the source used as corrosion test medium. Each fiher was stressed to 'if glass weakness. Ingles'* provided tbe mathematical work to 30,000 psi and tbe DI water was topped off once a year or ^ alculatc tbe stresses and strains caused hy typical scratches. ever>' otber year. DI water as the environment for the fiher test Tbese two researchers made predictions that were later conwas selected, because it is the most severe environment that lirmed experimentally. Tomozawa"* confirmed in 1980 the 50 could he imagined. The test continues. A radius tip predicted hy Ingles. Molecular modeling hy Cormack was presented in Wuhan, (."hina, in 2003. Cormack's modeling ofthe silica-glass structure showed ctxirdination changes and honding changes as he .sliced through successive thin layers o( the glass. On a molecular level, at a 5 A slice, a fragile and bumpy rather than a glassy, highly reflective surface appeared. Therefore, it appears that efforts to strengthen glass sbould he concentrated on the surface and only a few angstroms in depth. A solution to hritI leness is to heal the Griffith flaws and protect the glass surface I rom further damage. The chief technical officers of a major fiherglass manufaclurer witb experience in chemicals researcb has suggested to
Americon Coramic Society Bulletin, Vol. 86, No, 1

In another test, a 100 m glass fiber was measured to stretch 3 m when loaded to 150,000 psi of stress. Glass deflects under pressure, stretches under load, but returns to almost its original shape when stress is relieved. Glass is capable of withstanding incredible stresses and shape cbange in ways rarely envisionedif it is undamaged. Surfaces that are free of flaws seem to he tbe most important clue to solving the problem ofthe hrittleness in commercial glass.

Solving the Glass Strength Problem

An elegant solution to producing stronger glass is neeiied for all segments of glass manufacturing: container-glass, the
55

Producing Ultrastrong Glass

most challenged for profitability and survivability; flat-glass, for architectural and automotive applications, where weight reduction could be a direct benefit to energy efficiency; fiheri>lass, both textile and wool itisulation, to retain high R values; and specialty materials that include many glass products from tableware, laboratory ware, telecommunications, ophthalmic and other applications. The solution must be affordable and commercially applicable. In addition, the glass should be capable of being cut, shaped and bent with processes currently used. Strengthening processes, such as salt-bath chemical strengthening or sandwiching of high-expansion glass inside low-expansion glass, result in stronger glasses. However, they add considerable cost and limit future modification by the aforementioned processes and other cold-temperature reworking techniques. An invention that is affordable, commercially applicable and allows glass to achieve 500.000 psi MOR (3.4 GPa) is sought. The majority of glass failures originate at glass surfaces. What little is known about glass surfaces leads us to certain conclusions about what properties a modified surface must exhibit to meet new strength requirements. Hardness or abrasion resistance of the modified surface must approach that of the substrate glass in practical and commercial use. In most applications, the modified surface must be transparent and its index of refraction must match the substrate (to avoid interference colors). The modified surface must have chemical stability or resistance to environmental effects or commercial cleaning agents. A strong bond is essentialpreferably a covalent oxygen bond between glass and coating. In effect, the interface between the coating and the glass should be almost eliminated. Because water is considered the worst offender, a bydrophobic coating is needed to prevent future water attack of the surface glass structure. Surface healing of the Griffith flaws and protection of the healed surface sbould be accomplished with only nanometer thickness ot applied coatings.
Code 1801 Dec. 2006. rod under 150,000 psi stress for 70 years in

Breaking Stress of Annealed Glasst

Glass condition Surfaces ground and sandblasted Pressed articles Breaking stress (kpsi)

1.5-4.0

3-8
4-9 5-10 15-40

Ibwnware
Hot iron molds Paste molds Inner surfotes Drown tubing or rod Window-glass LCD [0.65 mm)* Fibers Annealed Freshly drawn Telecommunicotions fiber^

M5
8-20

-45

I MO 30-400 >I00

'Short-lime flexure tests in air IRel. 1). 'Because of its thickness, LCD never has been measured as a bar, but as sheet-glass using a ring-on-ring technique. This data, not taken Irom McLelland ond Shand, was previously published by Corning Inc. ^Corning Inc. advertised strength lor special fibers.

Sol-Gel Techniques
One technology that is operating at the boundary of inorganic and organic chemistry is the sol-gel process. The world of the inorganic scientist is challenged and perhaps renewed using chemical polymerization of inorganic glass networks. Rather than fusing silica and limestone and alkalies with heat, this low-temperature process begins by turning these raw materials into water-based gels. The molecules that are to become glass are tied up into a water-soluble polymer. As the gel dries, molecules detach from tbe polymer and react to form glass. When the gel is heated to low temperatures (300-500G), the remaining water is driven off. Sol-gel research efforts have focused initially on producing solid pieces.

A 30% titania-silica glass^"^ is an example of the power of sol--gel process to make things happen that do not happen in high-temperature melts. Titania is soluble to a maximum concentration of 10%, and. beyond that concentration, it phase separates and crystallizes as rutile. Surface-replica electron micrographs of 30% titania-silica glass show that it is possible to exceed the 10% solubility limit of titania in silica glass if it is produced using a sol-gel process near room temperatures. Therefore, use of a sol-gel in a thin film of exactly the same chemistry as the underlying glass should be considered. Thin films of nanometer thickness are affordable for use in commercial glasses and could potentially heal Griffith Flaws. To be a true glass, even as a thin film, the definition of glass also implies that the material be in a contiguous three-dimenAmerican Ceramic Society Builefin, Vol. 86, No. 1

56

.strucrure. It also often requires transparency, which precludes structural faults tir discontinuities in structure that would impair transmission of visible light. The homogeneous continuous phase previously could be obtained only in these systems through high-temperature melting. The sol-gel [irocess has overcome these barriers, at near-room-temperature conditions. Anyone who decides to pursue solving of the glass strength prohlcm .should consult the work of Yoldas as published frequently in tbe literature ofthe 1970s through the 1990s. Yoldas is tbe earliest researcher to pursue a polymerised inorganic glass structure nt low temperature. He continued to improve the prticess and was recognized for his accomplishments. Some initial attempts have heen made using sol-gel coatings to determine whether glass strength might be improved. In one sucb attempt, the glass chosen was Sisecam float glass In two thicknesses. Tbe coating work was accomplished in the Sisecam glass laboratories in Istanbul, Turkey. The work demonstrated tbe possible patb to solving tbe glass strength prohlem. All samples were tested for strength using tbe ringin-ring metbod at tbe Coming Inc. Researcb Laboratories in C'oming, N.Y. Tests were conducted in tbis first evaluation of sol-gel coatings. They revealed considerations for future tests:w Identify the tin bath surface and avoid damage hy rollers. Investigate better methods for laying down thin films of the laboratory samples. We are encouraged by the finished sampling completed and plan to prepare anotber sample with larger sample sizes.

700"

C ',

Sol-gel composed of 30% titania. At 70O''C, the 30% titania-silica is 30-40% porous. The sample consolidates and is dense when heated to 1000C. The sample phase separates and rutile crystallizes when heated ta 1400"C.

Tbe dream was replacing steel witb glass. Cooper^ argued that modem, glass-sbeathed buildings did not begin to tap the potential of their most visible component. Glass is intrin.siciilly strong, so strong, be said, that it sbould also he tbought of for structural support. To achieve the full potential of glass strength may require attention to three situations: surfaces, surfaces and surfaces: Complete knowledge of the surface and what occurs during tbe transition from molten glass to a rigid form is necessary. Tbis includes crinkling of the surface as well as attack from withoutand perhaps from witbinhy water vapor. Awareness of wbat is required to beal or repair tbe damaged surface st) tbat it is an integral, but invisible, part ofthe underlying structure is necessary. Realization of protection that is hard and abrasion-resistant but that is ductile and prevents moisture from reinjuring tbe healed surface is necessary.

Strong Glass
The Corning Glass Works lahoratories were actively studying glass strength 40 years ago. Tbe searcb was for long-chain polymeric silicates. Some appear to be metabolized in nature.

About the Author

lobn T Brown is Tecbnical Director of GMIC, Coming, N.Y.

Editor's Note
This article is based on a paper presented at the 1st Intemationat Congress on Ceramics. John Wiley & Sons, along witb ACerS, will publisb the ist International Congress on Ceramics Global Roadmap (hottk and CD-Rom), ISBN 0470104910 in January 2007. Order info at www.wiley , c om/go/ceram ies.

Three of 104 fibers beginning testing: (ieft) without DI wafer, (center) with a couple of inches of DI water and (right) fiber under load with complete 6 ft of fiber suspended in DI water. Design of the fixtures using stondord glass pipe couplings and a bottom plate are shown.

American Ceramic Society Bulletin, Vol. 86, No. 1

57 .