Strengthening of Glass Surfaces by Sulfur Trioxide Treatment

Mochel, Ellen L.; Nordberg, M. E.; Elmer, Thomas H.

doi:10.1111/j.1151-2916.1966.tb13173.x

Cited by 38 publications

(10 citation statements)

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“…The results clearly establish the inability of sub‐ T g heat treatment on the leached glass to return the surface to the original condition or to a true silica structure. However, due to the consolidation of the leached surface structure, the structural flaws and pathways for water ingress are reduced thereby potentially improving corrosion resistance and strength …”

Section: Discussionmentioning

confidence: 99%

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Effect of heat treatment on the surface chemical structure of glass: Oxygen speciation from in situ XPS analysis

et al. 2017

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Compositional changes in unleached and acid‐leached soda‐lime silicate surfaces were tracked with in‐vacuo heating and X‐ray Photoelectron Spectroscopy. Surface oxygen speciation was determined using a stoichiometry‐based algorithm via elemental composition, instead of the typical O 1s peak‐fitting approach. Accurate surface hydroxyl quantification is shown to require dehydration at temperatures near 200°C. On the unleached surface, no change in surface hydroxyl density (~2.5 OH/nm2) is observed in the temperature range of 200°C‐500°C after the initial dehydration. However, repolymerization in the network (non‐bridging oxygen→bridging oxygen) is observed due to volatilization of sodium. The acid‐leached surface undergoes sodium out‐diffusion from the bulk at sub‐Tg temperatures with laterally resolved inhomogeneity and shows a reduction in the concentration of hydroxyls from 4.5 OH/nm2 (200°C) to 3.2 OH/nm2 (500°C) accompanied by an increase in bridging oxygen. These results suggest that when [OH] > 2.5~3/nm2, vicinal OH undergo dehydroxylation with evolution of water, whereas when [OH] < 2.5/nm2, most OHs are non‐interacting and isolated (at temperatures below Tg). Furthermore, at temperatures exceeding 300°C, sodium has enough thermal energy to desorb in vacuum and diffuse from the bulk (depending on the abundance & local structure).

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Section: Discussionmentioning

confidence: 99%

“…However, due to the consolidation of the leached surface structure, the structural flaws and pathways for water ingress are reduced thereby potentially improving corrosion resistance and strength. 44,45…”

Section: Discussionmentioning

confidence: 99%

Effect of heat treatment on the surface chemical structure of glass: Oxygen speciation from in situ XPS analysis

et al. 2017

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“…This suggests that sulfur treatment might have some effect on suppressing the particle formation. Sulfur treatment has been known to have two effects: it can restrain the alkali elution from the surface of a glass vial due to dealkalization, 27,28) but it can also pit the surface of the vial and thus enhance delamination. 10,29) Considering the fact that sulfur treatment suppressed the particle formation, dealkalization might have an effect on the suppression of particle formation.…”

Section: Resultsmentioning

confidence: 99%

Effects of Phosphate Buffer in Parenteral Drugs on Particle Formation from Glass Vials

Ogawa

Miyajima

Wakiyama

et al. 2013

CHEMICAL & PHARMACEUTICAL BULLETIN

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The characteristics of inorganic particles generated in glass vials filled with phosphate buffer solutions were investigated. During storage, particles were visually detected in the phosphate buffer solution in particular glass vials which pass compendial tests of containers for injectable drugs. These particles were considered to be different from ordinal glass delamination, which has been reported in a number of papers because the particles were mainly composed of Al, P and O, but not Si. The formation of the particles accelerated at higher storage temperatures. Among the surface treatments tested for the glass vials, sulfur treatment showed a protective effect on the particle formation in the vials, whereas the SiO 2 coating did not have any protective effects. It was found that the elution ratio of Al and Si in the solution stored in the glass vials after the heating was similar to the ratio of Al and Si in borosilicate glass. However, the Al concentration decreased during storage (5°C, 6 months), and consequently, particle formation was observed in the solution. Adding citrate, which is a chelating agent for Al, effectively suppressed the particle formation in the heated solution. When 50 ppb and higher concentrations of Al ion were added to the phosphate buffer solution, the formation of white particles containing Al, P and O was detected. It is suggested that a phosphate buffer solution in a borosilicate glass vial has the ability to form particles due to interactions with the Al that is eluted from the glass during storage.Key words aluminum; borosilicate glass; tubing vial; aluminum phosphate complex The primary packaging system for a sterile drug product should provide adequate protection against any contamination from the external environment, and this protection should be assured during the entire shelf life of the product. In contrast, particularly for liquid, injectable drugs, components of the drugs are always in contact with the surface of the packaging component during storage. Therefore, during the course of formulation development of injectable drugs, it is essential to evaluate the physicochemical compatibility between the drug formulation and the packaging components to select appropriate primary packaging systems. 1,2) Among the packaging materials that are compatible with injectable drug solutions, glass containers, such as vials or ampoules, have been widely chosen and used. For parenteral drug products, borosilicate glasses (Type I) composed principally of silicon dioxide and boric oxides and soda-lime glasses composed of relatively high levels of sodium oxide and calcium oxide are used. Borosilicate glasses in particular are known to have a good chemical durability and are used commonly in the pharmaceutical industry as the primary container. However, these glass containers, even when made from borosilicate glasses, will unavoidably suffer some undesirable events from being in contact with the drug solutions in longterm storage. In certain cases, insoluble particle formation occurs in g...

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“…The surface compressive stress can greatly enhance modulus, hardness, and fracture toughness of glass. Other ways to improve glass surface strength include coatings, ion implantation, or heat treatment in an active gas . Also, glass mechanical properties could improved by eliminating surface flaws through annealing, etching, fire polishing, etc.…”

Section: Introductionmentioning

confidence: 99%

Thermal Poling of Soda‐Lime Silica Glass with Nonblocking Electrodes—Part 2: Effects on Mechanical and Mechanochemical Properties

Luo

Qian

et al. 2016

J. Am. Ceram. Soc.

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The mechanical and mechanochemical properties of soda lime silica (SLS) glass surfaces can vary with the sodium ion (Na + ) concentration in the subsurface region. Changes in these properties were studied upon modification of Na + concentrations in the SLS glass by thermal poling. In Part-1, it is found that the Na + -depleted and Na + -gradient layers could be formed at the anode and cathode sides, respectively. Here in Part-2, we show that Na + ions play a pivotal role in the mechanochemical wear property upon lateral shear stress. The Na + -depleted glass wear more readily as relative humidity (RH) increases, while Na + -gradient glass becomes resistant to wear at high RH. It is also found that the Na + -gradient glass surface has a higher elastic modulus and hardness with very little change in fracture toughness compared to the pristine surface. The Na + -depleted glass surface shows a lower elastic modulus and hardness; but its fracture toughness is significantly improved, which might be due to a larger densification capacity of Na + -depleted layer.

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Strengthening of Glass Surfaces by Sulfur Trioxide Treatment

Cited by 38 publications

References 1 publication

Effect of heat treatment on the surface chemical structure of glass: Oxygen speciation from in situ XPS analysis

Effect of heat treatment on the surface chemical structure of glass: Oxygen speciation from in situ XPS analysis

Effects of Phosphate Buffer in Parenteral Drugs on Particle Formation from Glass Vials

Thermal Poling of Soda‐Lime Silica Glass with Nonblocking Electrodes—Part 2: Effects on Mechanical and Mechanochemical Properties

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