Dealkalization
Encyclopedia
Dealkalization is a process of surface modification applicable to glass
es containing alkali
ions, wherein a thin surface layer is created that has a lower concentration of alkali ions than is present in the underlying, bulk glass. This change in surface composition commonly alters the observed properties of the surface, most notably enhancing corrosion
resistance.
Many commercial glass products such as containers are made of soda-lime glass
, and therefore have a substantial percentage of sodium
ions in their internal structure. Since sodium is an alkali element, its selective removal from the surface results in a dealkalized surface. A classic example of dealkalization is the treatment of glass containers, where a special process is used to create a dealkalized inside surface that is more resistant to interactions with liquid products put inside the container. However, the term dealkalization may also be generally applied to any process where a glass surface forms a thin surface layer that is depleted of alkali ions relative to the bulk. A common example is the initial stages of glass corrosion or weathering, where alkali ions are leached
from the surface region by interactions with water, forming a dealkalized surface layer.
A dealkalized surface may have either no alkali remaining or may just have less than the bulk. In silicate
glasses, dealkalized surfaces are also often considered “silica-rich” since the selective removal of alkali ions can be thought to leave behind a surface composed primarily of silica (SiO2). To be precise, dealkalization does not generally involve the outright removal of alkali from the glass, but rather its replacement with proton
s (H+) or hydronium
ions (H3O+) in the structure through the process of ion-exchange.
The most common example of its use with containers is on bottles intended to hold alcoholic spirits
. The reason for this is that some alcoholic spirits such as vodka
and gin
have an approximately neutral pH
and a high alcohol content, but are not buffered
in any way against changes in pH. If alkali is leached from the glass into the product, the pH will begin to rise (i.e. become more alkaline), can eventually reach a pH high enough that the solution begins to attack the glass itself quite effectively . By this mechanism, initially-neutral alcohol products can achieve a pH where the glass container itself begins to slowly dissolve, leaving thin, siliceous glass flakes or particles in the fluid. Dealkalization treatment hinders this process by removing alkali from the inside surface. Not only does this mean less extractable alkali in the glass surface directly contacting the product, but it also creates a barrier for the diffusion
of alkali from the underlying bulk glass into the product.
The same logic applies in pharmaceutical glass items such as vial
s that are intended to hold medicinal products. While many of these items are composed of more durable borosilicate glass
, they are also at times dealkalized in order to minimize the possibility of alkali leaching from the glass into the product. This action helps to avoid undesired changes in pH or ionic strength
of the solution, which not only inhibits eventual attack of the glass as previously described, but can also be important in maintaining the efficacy or stability of sensitive product formulations.
Historically, sulfur-containing compounds were the first materials used to dealkalize glass containers. Dealkalization proceeds through the interdiffusion/ion-exchange of Na+ out of the glass and H+/H3O+ into the glass, along with the subsequent reaction of the sulfate species with available sodium at the surface to form sodium sulfate (Na2SO4). The latter is left behind as water-soluble crystalline deposits, or bloom, on the glass surface that must be rinsed away prior to filling. On manufacturing lines, one way in which this process was done was by flooding the annealing lehr
with sulfur dioxide
(SO2) or sulfur trioxide
(SO3) gases—especially in the presence of water, which enhances the reaction. However, this practice fell into disfavor due to environmental and health concerns regarding SOx-type gases. An alternative method for sulfate treatment is with solid ammonium sulfate
salt or aqueous solutions thereof. These materials are introduced inside the container after forming and decompose into gases in the annealing lehr, where the resulting sulfur-containing gas mixture carries out the dealkalization reaction. This method is purportedly safer than flooding the annealing lehr since the unreacted components in the gas mixture will tend not to escape to the atmosphere, but rather react with each other and recreate the original salt in the container that can later be rinsed away.
Treatment with fluorine-containing compounds is typically accomplished through the injection of a fluorinated gas mixture (e.g. 1,1-difluoroethane mixed with air) into bottles at high temperatures. The gas can be delivered to the container either in the air used in the forming process (i.e. during the final blow of the container into its desired shape), or with a nozzle directing a stream of the gas down into the mouth of the bottle as it passes on a conveyor belt after forming but before annealing. The mixture gently combusts inside the bottle, creating an extremely small dose of hydrofluoric acid
that reacts with the glass surface and serves to dealkalize it. The resultant surface is virtually free from any residues of the process. This treatment is also known as the Ball I.T. process (I.T. standing for internal treatment) as Ball Corp.
held the patent and developed the first commercially available system implementing this process.
Routine tests for surface dealkalization in the glass container industry all generally aim to evaluate the amount of alkali extracted from the glass when it is rinsed with or exposed to purified water. For example, dealkalization can be quickly checked by introducing a small volume of distilled water to a freshly made bottle and rolling the bottle gently to pass the water completely over its inside surface. The pH of the rinse water is then measured; untreated containers will tend to yield a slightly alkaline pH in the 8-9 range due to extracted alkali, while dealkalized containers tend to yield a pH that remains approximately neutral.
A much more thorough version of this test is outlined in various international and domestic testing standards for glass containers , all with comparable methodologies. These tests evaluate the hydrolytic stability of the containers under more severe conditions, wherein containers, filled close to capacity with purified water, are covered and then heat-cycled in an autoclave
at 121°C for 1 hour. After cooling to room temperature, the water is titrated
with acid to evaluate the pH of the water, and therefore the equivalent amount of alkali extracted during the heat cycle. The alkali content of the rinse water can also be evaluated more directly by chemical analysis of the rinse water, as outlined in more recent versions of the European Pharmacopoeia. According to the Pharmacopoeia standards, internally-treated or dealkalized soda-lime glass containers are designated as "Type II" containers, thus setting them apart from their untreated counterparts due to their improved resistance to product interactions (as opposed to "Type III", which is standard, untreated soda-lime glass, or "Type I", which is reserved for highly resistant borosilicate glass).
While not routine, dealkalization can also be measured in a variety of other ways. Since dealkalized surfaces are more chemically durable, they are also more resistant to weathering reactions, and appropriate evaluation of this parameter can give indirect evidence of a previously dealkalized surface. It is also possible to evaluate dealkalization through the use of advanced, surface analytical techniques such as SIMS
or XPS
, which give direct measurements of glass surface composition.
Glass
Glass is an amorphous solid material. Glasses are typically brittle and optically transparent.The most familiar type of glass, used for centuries in windows and drinking vessels, is soda-lime glass, composed of about 75% silica plus Na2O, CaO, and several minor additives...
es containing alkali
Alkali
In chemistry, an alkali is a basic, ionic salt of an alkali metal or alkaline earth metal element. Some authors also define an alkali as a base that dissolves in water. A solution of a soluble base has a pH greater than 7. The adjective alkaline is commonly used in English as a synonym for base,...
ions, wherein a thin surface layer is created that has a lower concentration of alkali ions than is present in the underlying, bulk glass. This change in surface composition commonly alters the observed properties of the surface, most notably enhancing corrosion
Corrosion
Corrosion is the disintegration of an engineered material into its constituent atoms due to chemical reactions with its surroundings. In the most common use of the word, this means electrochemical oxidation of metals in reaction with an oxidant such as oxygen...
resistance.
Many commercial glass products such as containers are made of soda-lime glass
Soda-lime glass
Soda-lime glass, also called soda-lime-silica glass, is the most prevalent type of glass, used for windowpanes, and glass containers for beverages, food, and some commodity items...
, and therefore have a substantial percentage of sodium
Sodium
Sodium is a chemical element with the symbol Na and atomic number 11. It is a soft, silvery-white, highly reactive metal and is a member of the alkali metals; its only stable isotope is 23Na. It is an abundant element that exists in numerous minerals, most commonly as sodium chloride...
ions in their internal structure. Since sodium is an alkali element, its selective removal from the surface results in a dealkalized surface. A classic example of dealkalization is the treatment of glass containers, where a special process is used to create a dealkalized inside surface that is more resistant to interactions with liquid products put inside the container. However, the term dealkalization may also be generally applied to any process where a glass surface forms a thin surface layer that is depleted of alkali ions relative to the bulk. A common example is the initial stages of glass corrosion or weathering, where alkali ions are leached
Leaching (chemical science)
Leaching is the process of extracting minerals from a solid by dissolving them in a liquid, either in nature or through an industrial process. In the chemical processing industry, leaching has a variety of commercial applications, including separation of metal from ore using acid, and sugar from...
from the surface region by interactions with water, forming a dealkalized surface layer.
A dealkalized surface may have either no alkali remaining or may just have less than the bulk. In silicate
Silicate
A silicate is a compound containing a silicon bearing anion. The great majority of silicates are oxides, but hexafluorosilicate and other anions are also included. This article focuses mainly on the Si-O anions. Silicates comprise the majority of the earth's crust, as well as the other...
glasses, dealkalized surfaces are also often considered “silica-rich” since the selective removal of alkali ions can be thought to leave behind a surface composed primarily of silica (SiO2). To be precise, dealkalization does not generally involve the outright removal of alkali from the glass, but rather its replacement with proton
Proton
The proton is a subatomic particle with the symbol or and a positive electric charge of 1 elementary charge. One or more protons are present in the nucleus of each atom, along with neutrons. The number of protons in each atom is its atomic number....
s (H+) or hydronium
Hydronium
In chemistry, a hydronium ion is the cation , a type of oxonium ion produced by protonation of water. This cation is often used to represent the nature of the proton in aqueous solution, where the proton is highly solvated...
ions (H3O+) in the structure through the process of ion-exchange.
Motivation
For glass containers, the goal of surface dealkalization is to render the inside surface of the container more resistant to interactions with liquid products later put inside it. Since the treatment is directed primarily at changing the properties of the inside surface in contact with the product, it is also referred to as "internal treatment."The most common example of its use with containers is on bottles intended to hold alcoholic spirits
Alcohol
In chemistry, an alcohol is an organic compound in which the hydroxy functional group is bound to a carbon atom. In particular, this carbon center should be saturated, having single bonds to three other atoms....
. The reason for this is that some alcoholic spirits such as vodka
Vodka
Vodka , is a distilled beverage. It is composed primarily of water and ethanol with traces of impurities and flavorings. Vodka is made by the distillation of fermented substances such as grains, potatoes, or sometimes fruits....
and gin
Gin
Gin is a spirit which derives its predominant flavour from juniper berries . Although several different styles of gin have existed since its origins, it is broadly differentiated into two basic legal categories...
have an approximately neutral pH
PH
In chemistry, pH is a measure of the acidity or basicity of an aqueous solution. Pure water is said to be neutral, with a pH close to 7.0 at . Solutions with a pH less than 7 are said to be acidic and solutions with a pH greater than 7 are basic or alkaline...
and a high alcohol content, but are not buffered
Buffer solution
A buffer solution is an aqueous solution consisting of a mixture of a weak acid and its conjugate base or a weak base and its conjugate acid. It has the property that the pH of the solution changes very little when a small amount of strong acid or base is added to it. Buffer solutions are used as a...
in any way against changes in pH. If alkali is leached from the glass into the product, the pH will begin to rise (i.e. become more alkaline), can eventually reach a pH high enough that the solution begins to attack the glass itself quite effectively . By this mechanism, initially-neutral alcohol products can achieve a pH where the glass container itself begins to slowly dissolve, leaving thin, siliceous glass flakes or particles in the fluid. Dealkalization treatment hinders this process by removing alkali from the inside surface. Not only does this mean less extractable alkali in the glass surface directly contacting the product, but it also creates a barrier for the diffusion
Diffusion
Molecular diffusion, often called simply diffusion, is the thermal motion of all particles at temperatures above absolute zero. The rate of this movement is a function of temperature, viscosity of the fluid and the size of the particles...
of alkali from the underlying bulk glass into the product.
The same logic applies in pharmaceutical glass items such as vial
Vial
A vial is a relatively small glass vessel or bottle, especially used to store medication as liquids, powders or in other forms like capsules. They can also be sample vessels; e.g., for use in autosampler devices in analytical chromatography.The glass can be colourless or coloured, clear or amber...
s that are intended to hold medicinal products. While many of these items are composed of more durable borosilicate glass
Borosilicate glass
Borosilicate glass is a type of glass with the main glass-forming constituents silica and boron oxide. Borosilicate glasses are known for having very low coefficients of thermal expansion , making them resistant to thermal shock, more so than any other common glass...
, they are also at times dealkalized in order to minimize the possibility of alkali leaching from the glass into the product. This action helps to avoid undesired changes in pH or ionic strength
Ionic strength
The ionic strength of a solution is a measure of the concentration of ions in that solution. Ionic compounds, when dissolved in water, dissociate into ions. The total electrolyte concentration in solution will affect important properties such as the dissociation or the solubility of different salts...
of the solution, which not only inhibits eventual attack of the glass as previously described, but can also be important in maintaining the efficacy or stability of sensitive product formulations.
Dealkalization methods
Dealkalizing glass containers is accomplished by exposing the glass surface to reactive sulfur- or fluorine-containing compounds during the manufacturing process. A rapid ion-exchange reaction proceeds that depletes the inside surface of alkali, and is performed when the glass is at high temperature, usually on the order of 500-650°C or greater.Historically, sulfur-containing compounds were the first materials used to dealkalize glass containers. Dealkalization proceeds through the interdiffusion/ion-exchange of Na+ out of the glass and H+/H3O+ into the glass, along with the subsequent reaction of the sulfate species with available sodium at the surface to form sodium sulfate (Na2SO4). The latter is left behind as water-soluble crystalline deposits, or bloom, on the glass surface that must be rinsed away prior to filling. On manufacturing lines, one way in which this process was done was by flooding the annealing lehr
Lehr (glassmaking)
A lehr is a temperature-controlled kiln for annealing objects made of glass. The name derives from the German verb lehren meaning to teach and is cognate with the English lere also meaning to learn or acquire knowledge of ....
with sulfur dioxide
Sulfur dioxide
Sulfur dioxide is the chemical compound with the formula . It is released by volcanoes and in various industrial processes. Since coal and petroleum often contain sulfur compounds, their combustion generates sulfur dioxide unless the sulfur compounds are removed before burning the fuel...
(SO2) or sulfur trioxide
Sulfur trioxide
Sulfur trioxide is the chemical compound with the formula SO3. In the gaseous form, this species is a significant pollutant, being the primary agent in acid rain. It is prepared on massive scales as a precursor to sulfuric acid.-Structure and bonding:Gaseous SO3 is a trigonal planar molecule of...
(SO3) gases—especially in the presence of water, which enhances the reaction. However, this practice fell into disfavor due to environmental and health concerns regarding SOx-type gases. An alternative method for sulfate treatment is with solid ammonium sulfate
Ammonium sulfate
Ammonium sulfate , 2SO4, is an inorganic salt with a number of commercial uses. The most common use is as a soil fertilizer. It contains 21% nitrogen as ammonium cations, and 24% sulfur as sulfate anions...
salt or aqueous solutions thereof. These materials are introduced inside the container after forming and decompose into gases in the annealing lehr, where the resulting sulfur-containing gas mixture carries out the dealkalization reaction. This method is purportedly safer than flooding the annealing lehr since the unreacted components in the gas mixture will tend not to escape to the atmosphere, but rather react with each other and recreate the original salt in the container that can later be rinsed away.
Treatment with fluorine-containing compounds is typically accomplished through the injection of a fluorinated gas mixture (e.g. 1,1-difluoroethane mixed with air) into bottles at high temperatures. The gas can be delivered to the container either in the air used in the forming process (i.e. during the final blow of the container into its desired shape), or with a nozzle directing a stream of the gas down into the mouth of the bottle as it passes on a conveyor belt after forming but before annealing. The mixture gently combusts inside the bottle, creating an extremely small dose of hydrofluoric acid
Hydrofluoric acid
Hydrofluoric acid is a solution of hydrogen fluoride in water. It is a valued source of fluorine and is the precursor to numerous pharmaceuticals such as fluoxetine and diverse materials such as PTFE ....
that reacts with the glass surface and serves to dealkalize it. The resultant surface is virtually free from any residues of the process. This treatment is also known as the Ball I.T. process (I.T. standing for internal treatment) as Ball Corp.
Ball Corp.
Ball Corporation , originally Ball Brothers Glass Manufacturing Company, is an American company famous for producing glass canning jars. Founded in 1880, it is currently headquartered in Broomfield, Colorado. The company has expanded into other areas such as avionics, space systems, metal beverage...
held the patent and developed the first commercially available system implementing this process.
Testing for dealkalization
Routine tests for surface dealkalization in the glass container industry all generally aim to evaluate the amount of alkali extracted from the glass when it is rinsed with or exposed to purified water. For example, dealkalization can be quickly checked by introducing a small volume of distilled water to a freshly made bottle and rolling the bottle gently to pass the water completely over its inside surface. The pH of the rinse water is then measured; untreated containers will tend to yield a slightly alkaline pH in the 8-9 range due to extracted alkali, while dealkalized containers tend to yield a pH that remains approximately neutral.
A much more thorough version of this test is outlined in various international and domestic testing standards for glass containers , all with comparable methodologies. These tests evaluate the hydrolytic stability of the containers under more severe conditions, wherein containers, filled close to capacity with purified water, are covered and then heat-cycled in an autoclave
Autoclave
An autoclave is an instrument used to sterilize equipment and supplies by subjecting them to high pressure saturated steam at 121 °C for around 15–20 minutes depending on the size of the load and the contents. It was invented by Charles Chamberland in 1879, although a precursor known as the...
at 121°C for 1 hour. After cooling to room temperature, the water is titrated
Titration
Titration, also known as titrimetry, is a common laboratory method of quantitative chemical analysis that is used to determine the unknown concentration of an identified analyte. Because volume measurements play a key role in titration, it is also known as volumetric analysis. A reagent, called the...
with acid to evaluate the pH of the water, and therefore the equivalent amount of alkali extracted during the heat cycle. The alkali content of the rinse water can also be evaluated more directly by chemical analysis of the rinse water, as outlined in more recent versions of the European Pharmacopoeia. According to the Pharmacopoeia standards, internally-treated or dealkalized soda-lime glass containers are designated as "Type II" containers, thus setting them apart from their untreated counterparts due to their improved resistance to product interactions (as opposed to "Type III", which is standard, untreated soda-lime glass, or "Type I", which is reserved for highly resistant borosilicate glass).
While not routine, dealkalization can also be measured in a variety of other ways. Since dealkalized surfaces are more chemically durable, they are also more resistant to weathering reactions, and appropriate evaluation of this parameter can give indirect evidence of a previously dealkalized surface. It is also possible to evaluate dealkalization through the use of advanced, surface analytical techniques such as SIMS
Secondary ion mass spectrometry
Secondary ion mass spectrometry is a technique used in materials science and surface science to analyze the composition of solid surfaces and thin films by sputtering the surface of the specimen with a focused primary ion beam and collecting and analyzing ejected secondary ions...
or XPS
X-ray photoelectron spectroscopy
X-ray photoelectron spectroscopy is a quantitative spectroscopic technique that measures the elemental composition, empirical formula, chemical state and electronic state of the elements that exist within a material...
, which give direct measurements of glass surface composition.
See also
- Glass container industry
- GlassGlassGlass is an amorphous solid material. Glasses are typically brittle and optically transparent.The most familiar type of glass, used for centuries in windows and drinking vessels, is soda-lime glass, composed of about 75% silica plus Na2O, CaO, and several minor additives...
- Soda-lime glassSoda-lime glassSoda-lime glass, also called soda-lime-silica glass, is the most prevalent type of glass, used for windowpanes, and glass containers for beverages, food, and some commodity items...
- Surface scienceSurface scienceSurface science is the study of physical and chemical phenomena that occur at the interface of two phases, including solid–liquid interfaces, solid–gas interfaces, solid–vacuum interfaces, and liquid-gas interfaces. It includes the fields of surface chemistry and surface physics. Some related...
- Corrosion of glasses