Porous glass

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Porous glass is glass that includes pores, usually in the nanometre- or micrometre-range, commonly prepared by one of the following processes: through metastable phase separation in borosilicate glasses (such as in their system SiO2-B2O3-Na2O), followed by liquid extraction of one of the formed phases; [1] [2] through the sol-gel process; or simply by sintering glass powder.

Contents

The specific properties and commercial availability of porous glass make it one of the most extensively researched and characterized amorphous solids. Due to the possibility of modeling the microstructure, porous glasses have a high potential as a model system. They show a high chemical, thermal and mechanical resistance, which results from a rigid and incompressible silica network. They can be produced in high quality and with pore sizes ranging from 1 nm up to any desired value. An easy functionalization of the inner surface opens a wide field of applications for porous glasses.

A further special advantage of porous glasses compared to other porous materials, is that they can be made not only as powder or granulate, but also as larger pieces in almost any user defined shape and texture.

History

In the first half of the 20th century, Turner and Winks discovered that borosilicate glasses can be leached by acids. Their investigations showed that not only the chemical stability can be influenced by thermal treatment but also density, refractive index, thermal expansion and viscosity. In 1934, Nordberg and Hood[ clarification needed ] discovered that alkali borosilicate glasses separate in soluble (sodium borate rich) and insoluble (silica rich) phases if the glass is thermally treated. By extraction using mineral acids the soluble phase can be removed and a porous silica network remains. During a sintering process after extraction, a silica glass is generated, which has properties approaching those of quartz glass. The manufacturing of such high-silica glasses has been published as the VYCOR-process.

Definition

In scientific literature, porous glass is a porous material containing approximately 96% silica, which is produced by an acidic extraction or a combined acidic and alkaline extraction respectively, of phase separated alkali borosilicate glasses, and features a three-dimensional interconnected porous microstructure. For commercially available porous glasses, the terms porous VYCOR-Glass (PVG) and Controlled Pore Glass (CPG) are used. The pore structure is formed by a syndetic channel system and has a specific surface from 10 to 300 m²/g. Porous glasses can be generated by an acidic extraction of phase separated alkaliborosilica glasses, or by a sol-gel-process. By regulating the manufacturing parameters, it is possible to produce a porous glass with a pore size of between 0.4 and 1000 nm in a very narrow pore size distribution. You can generate various moulds, for example, irregular particles (powder, granulate), spheres, plates, sticks, fibers, ultra thin membranes, tubes and rings.

Manufacturing

Ternary Phase diagram in the sodium borosilicate system Phasendiagramm natriumborosilikat.jpg
Ternary Phase diagram in the sodium borosilicate system
Porous glass filled with water, sample about 1 mm thick, made by phase separation in a thermal gradient (high temperature on the right) of a sodium borosilicate glass, followed by acid leaching WetPorousGlass.jpg
Porous glass filled with water, sample about 1 mm thick, made by phase separation in a thermal gradient (high temperature on the right) of a sodium borosilicate glass, followed by acid leaching
Same porous glass as above, but dry. The increased difference between the refractive indices glass/air as compared to glass/water is causing greater whiteness based on the Tyndall effect. DryPorousGlass.jpg
Same porous glass as above, but dry. The increased difference between the refractive indices glass/air as compared to glass/water is causing greater whiteness based on the Tyndall effect.

Precondition for repetitious manufacturing of porous glass is the knowledge about structure determining and structure controlling parameters. The composition of the initial glass is a structure controlling parameter. The manufacturing of the initial glass, mainly the cooling process, the temperature and time of thermal treatment, and the after treatment are structure determining parameters. The phase diagram for sodiumborosilica glass shows a miscibility gap for certain glass compositions.

The upper critical temperature lies at about 760 °C and the lower one at about 500 °C. O.S. Moltschanova was the first person who exactly described the definition of the exsolution. For a phase separation the initial glass composition must lie in the miscibility gap of the ternary Na
2
O
-B
2
O
3
-SiO
2
glass system. By a thermal treatment, an interpenetration structure is generated, which results from a spinodal decomposition of the sodium-rich borate phase and the silica phase. This procedure is called primary decomposition. Using an initial glass composition, which lies on the line of anomaly, it is possible to attain a maximum decomposition, which is almost strainless.

As both phases have a different resistances to water, mineral acids, and inorganic salt solutions, the sodium-rich borate phase in these mediums can be removed by extraction. Optimal extraction is possible only if the initial glass composition and thermal treatment are chosen such that combine structures form, and not droplet structures. The texture is influenced by the composition of the initial glass, which directs size and type of decomposition areas. In the context of porous glasses, "texture" implies properties like specific pore volume, specific surface, pore size, and porosity. Furthermore, the texture of porous glasses is influenced by the concentration of the extraction medium and the ratio of fluid to solid. The emerging areas of decomposition depend on time and temperature of the thermal treatment.

Also, colloidal silica is solving in the sodium-rich borate phase, when time and temperature of thermal treatment are increased. This process is called secondary decomposition. The colloidal silica deposit in the macro pores during extraction and obscure the real pore structure. The solubility of colloidal silica in alkaline solutions is higher than network silica, and thus can be removed by an alkaline after-treatment.

Applications

Because of their high mechanical, thermal and chemical stability, variable manufacturing of pore sizes with a small pore size distribution and variety of surface modifications, a wide array of applications are possible. The fact that porous glasses can be produced in many different shapes is another advantage for application in industry, medicine, pharmacy research, biotechnology and sensor technology.

Porous glasses are ideal for material separation, because of the small pore size distribution. This is why they are used in gas chromatography, thin layer chromatography and affinity chromatography. An adaptation of stationary phase for a separation problem is possible by a specific modification of the surface of the porous glass.

In biotechnology, porous glasses have benefits for the cleaning of DNA and the immobilization of enzymes or microorganisms. Controlled pore glass (CPG) with pore sizes between 50 and 300 nm is also excellently suited for the synthesis of oligonucleotides. In this application, a linker, a nucleoside or a non-nucleosidic compound, is first attached to the surface of CPG. The chain length of produced oligonucleotides is dependent on the pore size of CPG.

In addition, porous glasses are used for manufacturing implants, especially dental implants, for which porous glass powder is processed with plastics to form a composite. The particle size and the pore size influence the elasticity of the composite so as to fit the optical and mechanical properties to surrounding tissue, for example, the appearance and hardness of dental enamel.

With the ability to form porous glasses as platelets, membrane technology is another important area of application. Hyper filtration of sea – and brackish water and ultra filtration in "downstream process" are but two. Additionally, they are often appropriate as a carrier for catalysts. For example, the olefin – metathesis was realized on the system metal – metal oxide/porous glass.

Porous glasses can be used as membrane reactors as well, again because of their high mechanical, thermal and chemical stability. Membrane reactors can improve conversion of limited balance reactions, while one reaction product is removed by a selective membrane. For example, in the decomposition of hydrogen sulfide on a catalyst in a glass capillary, the conversion by reaction was higher with glass capillary than without.

See also

Related Research Articles

Boron Chemical element, symbol B and atomic number 5

Boron is a chemical element with the symbol B and atomic number 5. In its crystalline form it is a brittle, dark, lustrous metalloid; in its amorphous form it is a brown powder. As the lightest element of the boron group it has three valence electrons for forming covalent bonds, resulting in many compounds such as boric acid, the mineral sodium borate, and the ultra-hard crystal boron carbide.

Borates are boron-oxygen compounds, which form boron oxyanions. These can be trigonal or tetrahedral in structure, or more loosely can consist of chemical mixtures which contain borate anions of either description. The element boron most often occurs in nature as borates, such as borate minerals and borosilicates.

High-performance liquid chromatography Technique used in analytical chemistry

High-performance liquid chromatography (HPLC), formerly referred to as high-pressure liquid chromatography, is a technique in analytical chemistry used to separate, identify, and quantify each component in a mixture. It relies on pumps to pass a pressurized liquid solvent containing the sample mixture through a column filled with a solid adsorbent material. Each component in the sample interacts slightly differently with the adsorbent material, causing different flow rates for the different components and leading to the separation of the components as they flow out of the column.

Pervaporation is a processing method for the separation of mixtures of liquids by partial vaporization through a non-porous or porous membrane.

Fused quartz Glass consisting of pure silica

Fused quartz,fused silica or quartz glass is a glass consisting of almost pure silica (silicon dioxide, SiO2) in amorphous (non-crystalline) form. This differs from all other commercial glasses in which other ingredients are added which change the glasses' optical and physical properties, such as lowering the melt temperature. Fused quartz, therefore, has high working and melting temperatures, making it less desirable for most common applications.

Refractory

A refractory material or refractory is a material that is resistant to decomposition by heat, pressure, or chemical attack, and retains strength and form at high temperatures. Refractories are polycrystalline, polyphase, inorganic, non-metallic, porous, and heterogeneous. They are typically composed of oxides or carbides, nitrides etc. of the following materials: silicon, aluminium, magnesium, calcium, and zirconium. Some metals with melting points >1850 °C like niobium, chromium, zirconium, tungsten, rhenium, tantalum, molybdenum etc. are also considered refractories.

In semiconductor manufacturing, a low-κ is a material with a small relative dielectric constant relative to silicon dioxide. Low-κ dielectric material implementation is one of several strategies used to allow continued scaling of microelectronic devices, colloquially referred to as extending Moore's law. In digital circuits, insulating dielectrics separate the conducting parts from one another. As components have scaled and transistors have gotten closer together, the insulating dielectrics have thinned to the point where charge build up and crosstalk adversely affect the performance of the device. Replacing the silicon dioxide with a low-κ dielectric of the same thickness reduces parasitic capacitance, enabling faster switching speeds and lower heat dissipation. In conversation such materials may be referred to as "low-k" rather than "low-κ" (low-kappa).

Borosilicate glass Glass made of silica and boron trioxide

Borosilicate glass is a type of glass with silica and boron trioxide as the main glass-forming constituents. Borosilicate glasses are known for having very low coefficients of thermal expansion, making them more resistant to thermal shock than any other common glass. Such glass is subjected to less thermal stress and can withstand temperature differentials without fracturing of about 165 °C (297 °F). It is commonly used for the construction of reagent bottles and flasks as well as lighting, electronics and cookware.

An artificial membrane, or synthetic membrane, is a synthetically created membrane which is usually intended for separation purposes in laboratory or in industry. Synthetic membranes have been successfully used for small and large-scale industrial processes since the middle of twentieth century. A wide variety of synthetic membranes is known. They can be produced from organic materials such as polymers and liquids, as well as inorganic materials. The most of commercially utilized synthetic membranes in separation industry are made of polymeric structures. They can be classified based on their surface chemistry, bulk structure, morphology, and production method. The chemical and physical properties of synthetic membranes and separated particles as well as a choice of driving force define a particular membrane separation process. The most commonly used driving forces of a membrane process in industry are pressure and concentration gradients. The respective membrane process is therefore known as filtration. Synthetic membranes utilized in a separation process can be of different geometry and of respective flow configuration. They can also be categorized based on their application and separation regime. The best known synthetic membrane separation processes include water purification, reverse osmosis, dehydrogenation of natural gas, removal of cell particles by microfiltration and ultrafiltration, removal of microorganisms from dairy products, and Dialysis.

Vycor is the brand name of Corning's high-silica, high-temperature glass. It provides very high thermal shock resistance. Vycor is approximately 96% silica and 4% boron trioxide, but unlike pure fused silica, it can be readily manufactured in a variety of shapes.

In materials science, the sol–gel process is a method for producing solid materials from small molecules. The method is used for the fabrication of metal oxides, especially the oxides of silicon (Si) and titanium (Ti). The process involves conversion of monomers into a colloidal solution (sol) that acts as the precursor for an integrated network of either discrete particles or network polymers. Typical precursors are metal alkoxides.

Bioglass 45S5 or calcium sodium phosphosilicate, is a bioactive glass specifically composed of 45 wt% SiO2, 24.5 wt% CaO, 24.5 wt% Na2O, and 6.0 wt% P2O5. Typical applications of Bioglass 45S5 include: bone grafting biomaterials, repair of periodontal defects, cranial and maxillofacial repair, wound care, blood loss control, stimulation of vascular regeneration, and nerve repair.

Aluminosilicate

Aluminosilicate minerals are minerals composed of aluminium, silicon, and oxygen, plus countercations. They are a major component of kaolin and other clay minerals.

Soda–lime glass Type of 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. Some glass bakeware is made of soda-lime glass, as opposed to the more common borosilicate glass. Soda–lime glass accounts for about 90% of manufactured glass.

Nanoporous materials

Nanoporous materials consist of a regular organic or inorganic bulk phase in which a porous structure is present. Nanoporous materials exhibit pore diameters that are most appropriately quantified using units of nanometers. The diameter of pores in nanoporous materials is thus typically 100 nanometers or smaller. Pores may be open or closed, and pore connectivity and void fraction vary considerably, as with other porous materials. Open pores are pores that connect to the surface of the material whereas closed pores are pockets of void space within a bulk material. Open pores are useful for molecular separation techniques, adsorption, and catalysis studies. Closed pores are mainly used in thermal insulators and for structural applications.

Glass-to-metal seal

Glass-to-metal seals are a very important element of the construction of vacuum tubes, electric discharge tubes, incandescent light bulbs, glass encapsulated semiconductor diodes, reed switches, pressure tight glass windows in metal cases, and metal or ceramic packages of electronic components.

Frustule Anatomical structure

A frustule is the hard and porous cell wall or external layer of diatoms. The frustule is composed almost purely of silica, made from silicic acid, and is coated with a layer of organic substance, which was referred to in the early literature on diatoms as pectin, a fiber most commonly found in cell walls of plants. This layer is actually composed of several types of polysaccharides.

Spin column-based nucleic acid purification

Spin column-based nucleic acid purification is a solid phase extraction method to quickly purify nucleic acids. This method relies on the fact that nucleic acid will bind to the solid phase of silica under certain conditions.

Thermoporometry and cryoporometry are methods for measuring porosity and pore-size distributions. A small region of solid melts at a lower temperature than the bulk solid, as given by the Gibbs–Thomson equation. Thus, if a liquid is imbibed into a porous material, and then frozen, the melting temperature will provide information on the pore-size distribution. The detection of the melting can be done by sensing the transient heat flows during phase transitions using differential scanning calorimetry – DSC thermoporometry, measuring the quantity of mobile liquid using nuclear magnetic resonance – NMR cryoporometry (NMRC) or measuring the amplitude of neutron scattering from the imbibed crystalline or liquid phases – ND cryoporometry (NDC).

Membrane technology covers all engineering approaches for the transport of substances between two fractions with the help of permeable membranes. In general, mechanical separation processes for separating gaseous or liquid streams use membrane technology.

References

  1. O. V. Mazurin (1984). Phase separation in glass. North-Holland. ISBN   0-444-86810-0.
  2. Werner Vogel (1994). Glass Chemistry (2 ed.). Springer-Verlag Berlin and Heidelberg GmbH & Co. K. ISBN   3-540-57572-3.