CA2525585C - Methods for producing low density products - Google Patents

Abstract

The method of preparing a low-density material and precursor for forming a low-density material. An aqueous mixture of inorganic primary component and a blowing agent is formed, the mixture is dried and optionally ground to form an expandable precursor. Such a precursor is then fired with activation of the blowing agent being controlled such that it is activated within a predetermined optimal temperature range. Control of the blowing agent can be accomplished via a variety of means including appropriate distribution throughout the precursor, addition of a control agent into the precursor, or modification of the firing conditions i.e. oxygen deficient or fuel rich environment, plasma heating etc.

Description

METHODS FOR PRODUCING LOW DENSITY PRODUCTS
Technical Field The present invention relates to methods of forming low density products and particularly methods and formulations for synthetically preparing engineered expanded microparticles.
Background of the Invention Any discussion of the prior art throughout the specification should in no way be considered as an admission that such prior art is widely known or forms part of common l0 general knowledge in the field.
Cenospheres are spherical inorganic hollow microparticles (microspheres) found in fly ash, which is produced as a by-product in coal-fired power stations.
Cenospheres typically make up around 1-2% of the fly ash and "harvested" cenospheres are widely commercially available. The composition, form, size, shape and density of cenospheres provide particular benefits in the formulation and manufacture of many low-density products.
One of the characterizing features of cenospheres is their exceptionally high chemical durability. This exceptionally high chemical durability is understood to be due to the very low content of alkali metal oxides, particularly sodium oxide, in their 2o composition. Accordingly, low-density composites produced from harvested cenospheres have the desirable properties of high strength to weight ratio and chemical inertness. Chemical inertness is especially important in Portland cement applications, where relative chemical inertness plays an important role in achieving highly durable cementitious products. Thus, harvested cenospheres have proven to be especially useful in building products and in general applications where they may come into contact with corrosive environments.
Despite the known utility of harvested cenospheres, their widespread use has been limited to a large extent by their cost and availability. The recovery of cenospheres in large quantities from fly ash is a labour intensive and expensive process.
Although it 3o is possible to increase the recovery of cenospheres from fly ash by modifying the collection process, the cost of improved recovery does not make this economically viable.

It may also be possible to alter combustion conditions in power stations to increase the yield of cenospheres in fly ash. However, combustion conditions in power stations are optimised for coal-burning rather than cenosphere production, and it is not economically viable to increase the yield of cenosphere production at the expense of coal-burning efficiency.
Several methods for producing microspheres are described in the prior art. An early method for manufacturing hollow glass microspheres involved combining sodium silicate and borax with a suitable foaming agent, drying and crushing the mixture, adjusting the size of the crushed particles and subsequently firing the particles. However, to this method suffers from the use of expensive starting materials (e.g.
borax). Hence, the resulting microspheres are necessarily expensive. In addition, the product has poor chemical durability due to a high percentage of sodium oxide in the resulting glass composition.
US 3,365,315 describes a method of producing glass microspheres from glass beads by heating in the presence of water vapour at a temperature of about 1200°C. This method requires the exclusive use of pre-formed amorphous glasses as the starting raw materials.
US 2,978,340 describes a method of forming glass microspheres from discrete, solid particles consisting essentially of an alkali metal silicate. The microspheres are 2o formed by heating the alkali metal silicate at a temperature in the range of 1000-2500°F
in the presence of a gasifying agent, such as urea or Na2C03.
US Patent Application No. 2001/0043996 (equivalent of EP-A-1156021) describes a spray combustion process for forming hollow microspheres having a diameter of from 1 to 20 microns. However, this process is unsuitable for malting hollow microspheres having a diameter similar to that of known cenospheres (i. e.
about 200 microns). In spray combustion processes, rapid steam explosion ruptures larger particles, thereby preventing formation of hollow microspheres greater than about 20 microns in diameter.
US Patent Application No. 2002/0025436 describes a process for forming solid 3o microspheres from fly ash. The process is said to improve the spheroidal uniformity of fly ash particles and provides fly ash spheroids having a density of about 1.8 g/cm3.
US 4,826,788 discloses a method of using two blowing agents activated at different temperatures to make large, foam glass granules greater than 1 mm in diameter.

However, the blowing agents discussed therein are limited to the blowing agents discussed therein are limited to one of the two agents must be an oxygen generating agent.
Generally speaking, prior art methods for forming engineered expanded microparticles involve firing an inorganic material in the presence o'f a blowing, gasifying or foaming agent.
Such blowing, gasifying or foaming agents should only be activated when the material from which the microparticle is produced, is in an appropriate form, ie liquid.
However, it is sometimes extremely difficult to match the blowing agent with the to material from which the microparticle will be formed and using the blowing agent in the most efficient manner.
It would be desirable to have a system which allowed a greater degree of control over the process.
It is an object of the present invention to overcome or ameliorate at least one of the disadvantages of the prior art, or to provide a useful alternative.
Summary of the Invention In a first aspect, the present invention provides a method of producing a low density material comprising:
providing a precursor by forming an aqueous mixture of an inorganic primary 2o component and a blowing component, drying the mixture and optionally grinding a predetermined particle size and firing the precursor to activate the blowing component to expand the precursor and form a low density material wherein activation of the blowing agent is controlled such that the blowing agent is activated within a predetermined optimal temperature range.
In a preferred embodiment, control of the blowing agent is accomplished by providing a control agent in the precursor which conserves and/or protects the blowing agent until the mixture reaches the aforementioned optimal temperature range.
The control agent can be provided in a number of forms. In one form, the control agents comprise materials which react under certain process conditions to alter the 3o environment of the precursor and thereby control activation of the blowing agent. For instance, control agents can be in the form of additional blowing agents. To explain, the precursor formulation can include a primary blowing agent which acts primarily to expand the precursor material and form the expanded microparticles. Control agents in the form of secondary and tertiary blowing agents may be included in the precursor mixture. These blowing agents can be activated at lower temperatures than the primary blowing agent. Many blowing agents are activated by oxidation. Activating tertiary and/or secondary blowing agents results in scavenging of oxygen from the process environment thereby controlling activation of the primary blowing agent. As will be clear to a person skilled in the art, this allows conservation and release of the primary blowing agent within the preferred optimal temperature range providing better control and more efficient use of the blowing agent in the process.
Control of the blowing agent can be accomplished by a variety of means. For 1o instance the process could be run within an oxygen deficient environment thereby reducing exposure of the blowing components to oxygen. When the precursor mixture reaches the optimal temperature range, oxygen could be introduced to the process to thereby activate the blowing agent.
Another alternative is to run the firing process in a fuel rich fashion, ie less oxidising. Other firing mechanisms such as plasma heating etc could be used with appropriate dosing of 02 depleting or 02 enriching gases to control activation of the blowing agent.
In still a further embodiment, conservation of the blowing agent can be accomplished physically. Distribution of the blowing agent throughout the precursor 2o particles can be such that at least some of the blowing component is maintained within the core of the precursor away from the surface. When such a precursor particle is subjected to heat, the surface temperature will rise and the core temperature will lag behind the surface temperature. This temperature differential will be engineered such that the blowing agent is activated only when substantially the entire precursor particle reaches the optimal temperature range.
In this regard, the optimal temperature range is one in which the precursor mixture reaches the optimal viscosity for the expansion process. The optimal temperature range will depend upon a number of parameters including the make up on the inorganic primary component, the make up of the blowing agents and control agents, 3o precursor particle size, desired density of resultant low density material.
Preferably, the low density material is produced in the form of microparticles, most preferably with a particle size of up to 1,000 microns.

In a second aspect the present invention provides a method of forming a precursor for a low density material comprising the steps of (a) providing au inorganic primary component;
(b) forming an aqueous mixture of the inorganic primary component, a blowing agent and a control agent, and;
(c) drying the mixture to provide an expandable precursor for forming a low density material wherein said blowing agent and control agent are selected to control activation of the blowing agent such that the blowing agent is activated within a predetermined optimal temperature range.
In a third aspect the present invention provides a method of forming a precursor for a low density material comprising the steps of:
(d) providing an inorganic primary component;
(e) forming an aqueous mixture of the inorganic primary component and a blowing agent; and (f) drying the mixture to provide an expandable precursor for forming a low density material wherein said blowing agent is selected and/or distributed in the precursor to control activation of the blowing agent upon firing of the precursor such that the blowing agent is activated 2o within a predetermined optimal temperature range.
In a fourth aspect the present invention provides a precursor suitable for producing expanded micro particles, said precursor comprising an expandable inorganic primary component, a blowing agent adapted to be activated and thereby expand said primary component, and a control agent selected to control activation of the blowing agent such that the blowing agent is activated within a predetermined optimal temperature range.
In a fifth aspect the present invention provides a precursor suitable for producing expanded micro particles, said precursor comprising an expandable inorganic primary component and a blowing agent selected and/or distributed within the precursor to control activation of the blowing agent whereby upon firing of the precursor to produce the expanded micro particles, the blowing agent is activated within a predetermined optimal temperature range.

In a sixth aspect the present invention provides a method of controlling activation of the blowing agent in an inorganic mixture to produce expanded micro particles, said method comprising:
providing at least one blowing agent which is activated under predetermined conditions to release a blowing gas and produce expanded micro particles and controlling such conditions whereby said activation takes place within a predetermined optimal viscosity range of the inorganic mixture.
In a seventh aspect the present provides a blowing component for producing expanded micro particles, said blowing component comprising a primary blowing agent to and a predetermined quantity of compatible control agent wherein upon inclusion of such a blowing component within an expandable mixture, the control agent may be activated prior or simultaneously with the blowing agent to control and conserve the blowing agent.
In a preferred embodiment, the control agent is activated at a lower temperature than the blowing agent. The control agent may act to alter the process environment and render it less conducive to activation of the blowing agent. For instance, the control agent may act to alter the oxygen content for scavenge oxygen from the process environment and thereby render such an environment less conducive to an oxidation activatable blowing agent.
2o In another preferred form, the blowing component/agent comprises a series of blowing compounds adapted to be sequentially activated over a range of process conditions.
In another embodiment, the present invention provides a method of controlling activation of a blowing agent in an inorganic mixture to produce expanded microparticles, said method comprising:
providing at least one blowing agent which is activated under predetermined conditions to release a blowing gas and produce expanded microparticles and controlling conditions such that said activation takes place within a predetermined optimal viscosity range of the inorganic mixture.
3o The inorganic mixture melts at relatively high temperatures. It is important that the blowing agent only be activated when the inorganic mixture is at is optimal viscosity, since, as will be clear to persons sltilled in the art, this will provide the greatest yield from the expansion process. Accordingly, the present invention provides a mechanism for tailoring the blowing agent such that it is activated at the optimal viscosity of the inorganic mixture, ie within a particular temperature range.
Unless the context clearly requires otherwise, throughout the description and the claims, the words 'comprise', 'comprising', and the like axe to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in the sense of "including, but not limited to".
As used herein, the term "engineered/expanded microparticle" means a hollow microparticle synthesized as a primary target product of a synthetic process.
The term does not include, for example, harvested cenospheres which are merely a by-product of io burning coal in coal-fired power stations.
Although the terms "microsphere" and "microparticle" axe used throughout the specification, it will be appreciated that these terms are intended to include any substantially rounded discrete microparticle, including those that are not true geometric spheres.
As used herein, the term "precursor" refers to the agglomerate or particle made from the suitable formulation prior to its expansion to form one or more expanded microparticles. The term "control agent" refers to a components included in the precursor which controls activation of the blowing component.
As used herein, the term "primary component" means that this component is usually the major constituent of the formulation/precursor, in the sense that the amount of primary component usually exceeds the amounts of the other constituents.
Moreover, the term "inorganic primary component" means that the primary component consists essentially of inorganic materials. However, small amounts (e.g. up to about 10 wt.%) of other materials may still be included in the inorganic primary component.
As used herein the term "activation" refers to the conditions, eg temperature, redox of the oxides present in the formulation, and gaseous atmosphere during thermal treatment ( e.g. oxygen partial pressure) range at which a blowing component is activated and releases its blowing gas.
The preferred method of the present invention advantageously provides a means 3o for producing expanded microparticles in excellent yield from widely available and inexpensive starting materials. Hence, the method, in its preferred form, reduces the overall cost of producing microparticles, and consequently increases the scope for their use, especially in the building industry, and all filler applications such as in polymeric _g_ .
t composites where the use of presently available cenospheres is relatively limited due to their prohibitive cost and low availability. The present invention recognises the critical importance of controlling activation of the blowing agents) in achieving reliable _ _ synthesis of expanded microparticles from a wide range of materials.
Preferred features of all aspects of the present invention are describe~~in more detail below.
Metlaod ofFo~naing Precursor to the Expa~rded Microparticle The precursor for producing the expanded microparticle can be produced by combining the primary component, blowing component and optionally, control agent in to an aqueous mixture. This aqueous mixture is then dried to produce an agglomerated precursor.
As described above, the present invention provides a method of forming a precursor, which includes the steps of mixing and drying. The resultant precursor is generally a substantially solid agglomerate mixture of its constituent materials.
15 Typically, the mixing step provides an aqueous dispersion or paste, which is later dried. Mixing can be performed by any conventional means used to blend ceramic powders. Examples of preferred mixing techniques include, but are not limited to, agitated tanks, ball mills, single and twin screw mixers, and attrition mills.
Certain mixing aids (e.g. surfactants) may be added in the mixing step, as 2o appropriate. Surfactants, for example, may be used to assist with mixing, suspending and dispersing the particles.
Drying is typically performed at a temperature in the range of 30 to 600°C and may occur over a period of up to about 4~ hours, depending on the drying technique employed. Any type of dryer customarily used in industry to dry slurnes and pastes may 25 be used in the present invention.
Drying may be performed in a batch process using, for example, a stationary dish or container. Alternatively, drying may be performed in a spray dryer, fluid bed dryer, rotary dryer, rotating tray dryer or flash dryer.
Preferably, the mixture is dried such that the water content of the resultant 3o agglomerate precursor is less than about 14 wt.%, more preferably less than about 10 wt.%, more preferably less than about 5 wt.%, and more preferably about 3 wt.%
or less.
It was found that with 14 wt.% water or more in the precursor, it tends to burst into fines upon firing. It is understood by the present inventors that this bursting is caused by rapid steam explosion in the presence of too much water.
Hence, the resultant precursor should preferably be essentially dry, although a small amount of residual moisture may be present after the solution-based process for its formation. Indeed, a small amount of water may help to bind particles in the precursor together, especially in cases where particles in the precursor are water-reactive.
Preferably, the dried precursor particles have an average particle size in the range of 10 to 1000 microns, more preferably 30 to 1000 microns, more preferably 40 to 500 microns, and more preferably 50 to 300 microns. The particle size of the precursor will 1o be related to the particle size of the resultant synthetic hollow microsphere, although the degree of correspondence will, of course, only be approximate. If necessary, standard comminuting/sizing/classification techniques may be employed to achieve this preferred average particle size.
Drying is most preferably performed using a spray dryer having an aqueous feed.
It has been found that spray drying has several advantages when used in the present invention.
Method o Formih~ Precursor Usin~~Sp~ay D
As discussed above, the present invention envisages various techniques for controlling activation of the blowing agent such that it is activated at the optimum point 2o in the production process. Such control can be achieved by combining a control agent in the precursor formulation. Another embodiment includes a series of control agents and/or blowing agents such that there is sufficient blowing/expanding gas available at the optimal temperature. In one embodiment, a series of blowing agents may be used which are sequentially activated as temperature rises.
Yet a further embodiment involves distributing the blowing agent throughout the precursor such that while the precursor is being fired, the blowing agent distributed near the surface is exposed to a high temperature but the blowing agent near the core of the precursor is "physically" protected. To explain, the thermal conductivity of the formulation causes a delay between application of heat on the surface of the precursor to 3o temperature rise within the core of the precursor. Accordingly, blowing agent which is within the core of the precursor will not be activated until a major portion of the precursor particle has already reached its optimal temperature.

Still further, as discussed above, many blowing agents are activated by oxidation.
Particles within the core of the precursor will not be exposed to oxygen to the same extent as blowing agent on the surface, further protecting the blowing agent in the core of the particle.
Rather surprisingly, the Applicant has found that spray dryers are not only useful for forming precursors to the expanded microparticles but are also excellent at providing the aforementioned optimal distribution of the blowing agent within the precursor. Not wishing to be bound by any particular theory, it would appear that blowing agents which are water soluble tend to come to the surface during the spray dry production technique.
1o Non water soluble blowing agents tend to remain within the core.
Accordingly, one can design a mixture of blowing agents which provide initial, subsequent and final activation according to their water solubility. An example may be sugar which is useful as a blowing agent but is water soluble. During the spray dry technique, this blowing agent will tend to migrate to the surface of the precursor. Silicone carbide on the other hand, 15 which is also a useful blowing agent is non water soluble and does not migrate to the surface of the precursor.
Spray dryers are described in a number of standard textbooks (e.g. Industrial Drying Equipment, C.M. van't Land; Handbook of Industrial Drying 2"'~ Edition, Arun S. Mujumbar) and will be well known to the skilled person.
2o In addition to the aforementioned advantages, it is generally desirable to synthesize expanded microparticles having a predetermined average particle size and a predetermined (preferably narrow) particle size distribution. The use of a spray dryer in the present invention has been found to reduce the need for any sizing/classification of the precursors or, ultimately, the synthetic expanded microparticles. Spray drying has the 25 additional advantage of allowing a high throughput of material and fast drying times.
Hence, in a particularly preferred embodiment of the present invention, the drying step is performed using a spray dryer.
It has been determined that the particle size and particle size distribution can be affected by one or more of the following parameters in the spray drying process:
30 - inlet slurry pressure and velocity (particle size tends to decrease with increasing pressure);
design of the atomizer (rotary atomizer; pressure nozzle, two fluid nozzle or the like) design of the gas inlet nozzle;
volume flow rate and flow pattern of gas; and slurry viscosity and effective slurry surface tension.
Preferably, the aqueous slurry feeding the spray dryer comprises 25 to 75% w/v solids, more preferably 40 to 60% w/v solids.
In addition to the ingredients described above, the aqueous slurry may contain further processing aids or additives to improve mixing, flowability or droplet formation in the spray dryer. Suitable additives are well known in the spray drying art.
Examples of such additives are sulphonates, glycol ethers, cellulose ethers and the like. These may 1o be contained in the aqueous slurry in an amount ranging from 0 to 5 % w/v.
In the spray drying process, the aqueous slurry is typically pumped to an atomizer at a predetermined pressure and temperature to form slurry droplets.
The atomizer may be one or a combination of the following: an atomizer based on a rotary atomizer (centrifugal atomization), a pressure nozzle (hydraulic atomization), or a two-fluid pressure nozzle wherein the slurry is mixed with another fluid (pneumatic atomization).
In order to ensure that the droplets formed are of a proper size, the atomizer may also be subjected to cyclic mechanical or sonic pulses. The atomization may be performed from the top or from the bottom of the dryer chamber. The hot drying gas 2o may be injected into the dryer co-current or counter-current to the direction of the spraying.
It has been found that by controlling the spray drying conditions, the average particle size of the precursors and the precursor particle size distribution can be controlled. For example, a rotary atomizer has been found to produce a more uniform agglomerate particle size distribution than a pressure nozzle. Furthermore, rotating atomizers allow higher feed rates, suitable for abrasive materials, with negligible blockage or clogging. In some embodiments, a hybrid of lrnown atomizing techniques may be used in order to achieve agglomerate precursors having the desired characteristics.
The atomized droplets of slurry are dried in the spray dryer for a predetermined residence time. The residence time can affect the average particle size, the particle size distribution and the moisture content of the resultant precursors. The residence time is preferably controlled to give the preferred characteristics of the precursor, as described above. The residence time can be controlled by the water content of the slurry, the slurry droplet size (total surface area), the drying gas inlet temperature and gas flow pattern within the spray dryer, and the particle flow path within the spray dryer.
Preferably, the residence time in the spray dryer is in the range of 0.1 to 10 seconds, although relatively long residence times of greater than 2 seconds are generally more preferred.
Preferably, the inlet temperature in the spray dryer is in the range of 300 to 600°C and the outlet temperature is in the range of 90 to 220°C.
Spray drying advantageously produces precursors having this narrow particle size distribution. Consequently, synthetic expanded microparticules resulting from these to precursors will have a similarly narrow particle size distribution and consistent properties for subsequent use.
A further surprising advantage of using a spray dryer is that the resultant precursors have an improved infra-particle distribution of constituents. Wlule the atomized droplets are resident in the spray dryer, water is rapidly pulled from the interior to the exterior, thus forming a concentration gradient of soluble species in the agglomerate, with relatively water-soluble species being more concentrated towards the exterior. Another advantage of spray drying is to form dried cellulated agglomerated precursors according to the method of present invention (e.g. pre-foaming).
The entrained gas will further expand during the foaming process to lower the density of the 2o product which otherwise may not have been possible to achieve with multi blowing agents. By this optional and yet novel method, low temperature gas forming compounds are added to the precursor before the drying process. The gas forming compound can be activated either by physical means such as degassing due to a reduction in surface tension (reverse temperature solubility), or by chemical means. An example of chemical gasification at low temperature is decomposition of carbonates to C02 by changing the pH, or use of appropriate organic compounds such as air entraining agents customarily used in concrete.
For an efficient and reliable synthesis of hollow microspheres, the precursor should ideally have a high concentration of glass-forming material at the surface, which 3o can form a molten glassy skin during firing. Furthermore, the precursor should ideally have a concentration of blowing agent near the core, which can release a blowing gas for entrapment within the glassy skin during firing. With careful selection of materials, this ideal infra-particle distribution can be achieved using the spray drying method.

Inorganic P~imary Component Preferably, the amount of inorganic primary component comprises at least 40 wt.% based on the total dry weight of the agglomerate precursor, more preferably at least 50 wt.%, more preferably at least 60 wt.%, more preferably at least 70 wt.%
and more preferably at least 80 wt.%.
The preferred ratio of primary component to other components, eg blowing agent will vary, depending on the composition of each of these ingredients.
Typically, the ratio of primary component to blowing agent will be in the range of 1000:1 to 10:1, more preferably, 700:1 to 15:1, and more preferably 500:1 to 20:1.
to Preferably, the inorganic primary component comprises at least one material selected from inorganic oxides, non-oxides, salts or combinations thereof.
Such materials may be industrial and/or residential by-products, minerals, rocks, clays, technical grade chemicals or combinations thereof. One of the advantages of the present invention is that it allows the synthesis of hollow microspheres from inexpensive industrial and/or residential waste products. Accordingly, the inorganic primary component may comprise materials such as fly ash, bottom ash, blast-furnace slag, paper ash, waste glasses (e.g. soda lime glasses, borosilicate glasses or other waste glasses), waste ceramics, kiln dust, waste fibre cement, concrete, incineration ash, diatomaceous earth, silica sand, silica fume, or combinations thereof.
. Preferably, the inorganic primary component is capable of forming a viscoelastic liquid when heated to a predetermined temperature. This viscoelastic liquid is preferably a glass-forming liquid.
Preferably, the inorganic primary component comprises at least one compound in an oxide form, which can form a majority of a glass phase. Non-oxide components may oxidize and become part of the glass phase, except for those elements that can remain dissolved but not oxidized, such as halides.
In one preferred embodiment, the inorganic primary component comprises at least one silicate material. Silicate materials are well known to the person slcilled in the art. Generally, these are materials having a relatively large component of silica (SiOa) (i.e. greater than about 30 wt.%, preferably greater than 50% and more preferably greater than 60%). In most cases alumina is also a major oxide constituents of the silicate materials. The term of silicate in the present invention, hence covers all the aluminosilicate materials suitable as primarily compounds.

The amounts of silica and alumina in the silicate material will vary depending on the source and may even vary within the same source. Fly ash, for example, will contain varying amounts of silica and alumina depending on the type of coal used and combustion conditions. Preferably, the mass ratio of silica (Si02) to alumina (A1203) is greater than about 1. Typically, silicate materials for use in this preferred embodiment of the present invention have a composition of 30 to 95 wt.% Si02; 0 to 45 wt.%
(preferably 2 to 45 to wt.%) A1203; up to about 30 wt.% (preferably up to about 15 wt.%) divalent metal oxides (e.g. MgO, CaO, SrO, Ba0); up to about 50 wt.%
monovalent metal oxides (e.g. Li20, Na20, Kz0); and up to about 20 wt.% of other 1o metal oxides, including metal oxides which exist in multiple oxidation states (e.g. Sn02, Mn02, Fez03 etc.).
Typical silicates, which may be used in this embodiment of the present invention are fly ash (e.g. Type F fly ash, Type C fly ash etc.), waste glass, bottom ash, blast-furnace slag, paper ash, basaltic rock, andesitic rock, feldspars, silicate clays (e.g.
15 kaolinite clay, illite clay, bedalite clay, bentonite clay, china, fire clays etc.), bauxite, obsidian, volcanic ash, volcaiuc rocks, volcanic glasses, geopolymers or combinations thereof.
Silicates, such as those described above, may form the majority of the inorganic primary component. For example, silicates may form at least 50 wt.%, at least 70 wt.%, 20 or at least 90 wt.% of the inorganic primary component, based on the total weight of the inorganic primary component.
Fly ash, waste soda lime glass, andesitic rock, basaltic rock and/or clays are preferred source materials for the inorganic primary component. Fly ash is a particularly preferred inorganic primary component due to its low cost and wide availability. In one 25 form of the invention, the primary component comprises at least 5 wt.% fly ash, and more preferably at least 10 wt.% fly ash, based on the total amount of primary component. In another form of the invention, the inorganic primary component comprises at least 50 wt.% fly ash, at least 70 wt.% fly ash, or at least 90 wt.% fly ash, based on the total amount of inorganic primary component. In some embodiments of the 3o present invention, the inorganic primary component may include a geopolymer, which is formed when a silicate is contacted with an aqueous solution of a metal hydroxide (e.g.
NaOH or KOH). Geopolymers are well known in the art.

The inorganic primary component may be either calcined or non-calcined. The term "calcined" means that the inorganic material has been heated in air to a predetermined calcination temperature for a predetermined duration so as to either oxidise or pre-react certain component(s). Calcination of the inorganic material may be advantageous in the present invention since the blowing (expansion) process can be sensitive to the redox state of multivalent oxides) present in the inorganic material.
Without wishing to be bound by theory, it is believed that activation of the blowing agents is influenced by the release of oxygen from multivalent oxides) present in the inorganic material (e.g. by redox reaction). As an example, a carbonaceous blowing l0 agent may react with oxygen released from ferric oxide (Fea03) to form COX, (where x can be 1 or 2 depending on carbon oxidation state)which is in turn reduced to ferrous oxide (Fe0). The release of COX from the blowing agent expands the microsphere.
Hence, by pre-calcinating the inorganic material in air, the relative amount of ferric oxide is increased, which is then used as a source of oxygen for blowing agents to produce more gas, thereby lowering the density of the microparticles.
W addition, calcination can promote pre-reaction of oxide components and/or cause partial vitrification in the inorganic material, which may be beneficial in the production of high quality microparticles.
In cases where high chemical durability is required, the primary inorganic 2o component is preferably a low alkali material. By "low alkali material", it is meant a material having an alkali metal oxide content of less than about 10 wt.%. In this form of the present invention, nay high alkali materials may still be included in the inorganic primary component. Accordingly, waste glass powders, such as soda lime glasses (sometimes referred to as Gullet) having an alkali content of up to about 15 wt.%
may be included.
Preferably, the inorganic primary component has an average primary particle size in the range of 0.01 to 100 microns, more preferably 0.05 to 50 microns, more preferably 0.1 to 25 microns, and more preferably 0.2 to 10 microns. Preferred particle sizes may be achieved by appropriate grinding and classification. All types of grinding, milling, 3o and overall size reduction techniques that are used in ceramic industry can be used in the present invention. Without limiting to other methods of size reduction used for brittle solids, preferred methods according to the present invention are ball milling (wet and dry), high energy centrifugal milling, jet milling, and attrition milling. If more than one inorganic material is to be used, then the multitude of ingredients can be co-ground together. In one method of the present invention, all the constituent materials of the agglomerate precursor are co-ground together before mixing (e.g. in a wet ball mill).
Blowin~LCornpo~ent The blowing agents used in the present invention are compounds which, when heated, liberate a blowing gas by one or more of combustion, evaporation, sublimation, thermal decomposition, gasification or diffusion. The blowing gas may be, for example, C02, CO, 02, N2, N20, NO, N02, 502, S03 H20 or mixtures thereof. Preferably, the blowing gas comprises C02 and/or CO.
l0 Preferably, the amotuit of blowing component is in the range of 0.05 to 10 wt.%
based on the total dry weight of the precursor, more preferably 0.1 to 6 wt.%, and more preferably 0.2 to 4 wt.%. The exact amount of blowing component will depend on the composition of the inorganic primary component, the types of blowing agents and the required density of the final hollow microsphere.
15 In one embodiment, the blowing component comprises a primary blowing agent and a secondary blowing agent. The primary blowing agent has a first activation temperature and the second blowing agent has a second activation temperature lower than the first activation temperature. In other words, in use, the secondary blowing agent is initially activated as temperature rises followed by the primary blowing agent.
2o This conserves the primary blowing agent.
Preferably, the primary blowing agent is selected from powdered coal, carbon black, activated carbon, graphite, carbonaceous polymeric organics, oils, carbohydrates such as sugar, corn syrup, starch; PVA, various amines, carbonates, carbides (e.g. silicon carbide, aluminium carbide), sulfates, sulfides, nitrides (aluminium nitride, silicon 25 nitride, boron nitride), nitrates, polyols, glycols, glycerine or combinations thereof.
Silicon carbide and carbon black are particularly preferred primary blowing agents.
Preferably, the secondary blowing agent is selected from, carbon, carbonaceous polymeric organics, oils, carbohydrates such as sugar, corn syrup, starch;
PVA, various amines, carbonates, sulfates, sulfides, nitrides, nitrates, polyols, glycols, glycerine or 3o combinations thereof. Carbon black, sugar, corn syrup and starch are particularly preferred secondary blowing agents.
In alternative embodiments of the present invention, the blowing component comprises further blowing agents, in addition to the primary and secondary blowing agents described above. These additional blowing agents are designated tertiary, quaternary etc. blowing agents having corresponding third, fourth etc.
activation temperatures.
Accordingly, in one alternative embodiment the blowing component further comprises a tertiary blowing agent having a third activation temperature, wherein the third activation temperature is less than the first activation temperature.
Preferably, the third activation temperature is also less than the second activation temperature. The tertiary blowing agent may be selected from carbonaceous polymeric organics, oils, carbohydrates such as sugar, corn syrup, starch; PVA, various amines, sulfates, sulfides, 1o nitrides, nitrates, polyols, glycols, glycerine or combinations thereof.
Sugar, corn syrup, and starch are particularly preferred tertiary blowing agents.
Preferably, and particularly if the blowing agent is non-water soluble, the blowing agent has an average particle size of about 10 microns.
The use of multiple blowing agents has been shown to have particular benefits in the synthesis of expanded microparticles. It provides control of the blowing (expansion) process, thereby allowing a reliable synthesis of expanded microparticles from a wide range of readily available and inexpensive inorganic materials. Furthermore, it maximises the efficiency of high quality (and relatively expensive) primary blowing agents, which further reduces the cost of synthetically manufacturing expanded 2o microparticles.
Without wishing to be bound by theory, it is believed that the primary blowing agent produces the majority of gas during the blowing (expansion) process when the precursor. The secondary (and, optionally, tertiary, quaternary etc.) blowing agent acts as a sacrificial material by reducing or preventing premature spending of the primary blowing agent, for example by vaporisation and/or oxidation, before the precursor material has become molten enough to capture the blowing gas during the expansion process.
For instance, a preferred blowing agent composition includes silicon carbide as a primary blowing agent and carbon or powdered coal as a secondary blowing agent.
3o Carbon acts as the sacrificial blowing agent and starts to oxidize first keeping oxygen away from carbide until the precursor melts. Once the precursor melts, the majority of CO and C02 gas produced by oxidation of carbide is trapped within the molten precursor.

An alternative blowing agent composition comprises silicon carbide as the primary blowing agent, carbon as the secondary blowing agent, and sugar as the tertiary blowing agent. Without wishing to be bound by theory, it is believed that sugar starts to oxidize first preventing oxidation of carbon and carbide, then carbon begins to oxidize preventing oxidation of carbide, and then finally carbide oxidizes to CO and COZ, which are primarily responsible for blowing (expansion) of the microparticle. One advantage of the present method of invention is to reduce the overall cost of the blowing agent. Sugar is less costly than carbon, and silicon carbide is by far much more expensive than either one. By using the multi blowing agents, the amount of expensive silicon carbide 1 o required to produce a given low density product is dramatically reduced.
Figure 2 depicts the TGA (thermal gravimetric analysis) of sugar, carbon, and silicon carbide in air. The activation temperatures with ascending order start with sugar, then carbon, and finally silicon carbide.
This novel mixture of blowing agents allows the use of inexpensive sacrificial blowing agents (e.g. sugar, carbon and/or powdered coal), in order to maximise the efficiency and blowing capacity of a more expensive primary blowing agent (e.g. silicon carbide).
As discussed earlier, an additional and important advantage is realised when the precursors are prepared using the spray drying method. By making use of the mechanism 2o described above, whereby relatively water-soluble species are pulled towards the exterior of the precursor during spray drying, an advantageous intra-particle distribution of primary and secondary blowing agents can be achieved.
Hence, using a relatively water-insoluble primary blowing agent and a relatively water-soluble secondary blowing agent, the secondary blowing agent can migrate towards the surface of the precursor, leaving the primary blowing agent uniformly dispersed. With the primary and secondary blowing agents separated in this way, the secondary blowing agent can more effectively "scavenge" oxygen away from the primary blowing agent in the critical period during firing in which a glassy skin has not yet formed around the precursor. This scavenging effect protects the primary blowing 3o agents against premature spending, thereby maximising its blowing capacity after (or during) formation of the glassy skin.
Sugar is an example of a useful secondary blowing agent. Sugar is soluble in water and will migrate towards the exterior of the precursor during spray drying. At the same time, sugar can be converted to carbon at the spray drying temperature, resulting in a fine dispersion of carbon particles throughout the exterior part of the precursor. This fine dispersion of carbon particles acts as an effective secondary (sacrificial) blowing agent by scavenging oxygen away from a primary blowing agent (e.g. silicon carbide) during the initial period of firing.
Furthermore, organic compounds, such as sugar and starch, help to bind the agglomerate precursor constituents together. Thus, materials such as sugar and starch can act as both binding agents and blowing agents in the present invention.
Control A~efZt 1o The secondary and tertiary blowing agents mentioned above act as control agents to protect and conserve the primary blowing agent in the precursor:formulation. Persons skilled in the art will be aware of other materials which can be include in the precursor formulation and which can act to control activation of the blowing agent by, for example, scavenging oxygen in the process environment.
Bi~~eht In a preferred embodiment of the present invention, a binding agent/ agents (or binder) may be mixed with the inorganic primary component and blowing component.
The primary function of the binding agent is to intimately bind the silicate particles in the precursor together. The binder also may be selected to react with the silicate 2o materials to lower the viscosity of the resulting glassy microparticles at the firing temperature.
In general, any chemical substance that is reactive and/or adheres with the inorganic primary component can be used as the binding agent. The binder may be any commercially available material used as a binder in the ceramic industry.
Preferably, the binding agent is selected from alkali metal silicates (e.g.
sodium silicate), alkali metal aluminosilicates, alkali metal borates (e.g. sodium tetraborate), alkali or alkaline earth metal carbonates, alkali or alkaline earth metal nitrates, alkali or allcaline earth metal nitrites, boric acid, alkali or allcaline earth metal sulfates, alkali or alkaline earth metal phosphates, alkali or alkaline earth metal hydroxides (e.g. NaOH, 3o KOH or Ca(OH)Z), carbohydrates (e.g. sugar, starch etc.), colloidal silica, inorganic silicate cements, Portland cement, lime-based cement, phosphate-based cement, organic polymers (e.g. polyacrylates) or combinations thereof. In some cases, fly ash, such as ultrafine, Type C or Type F fly ash, can also act as a binding agent.

The binding agent and blowing agent are typically different from each other, although in some cases (e.g. sugar, starch etc.) the same substance may have dual blowing/binding agent properties, as described above.
The term "binder" or "binding agent", as used herein, includes all binding agents mentioned above, as well as the in situ reaction products of these binding agents with other components in the agglomerate. For example, an alkali metal hydroxide (e.g.
NaOH) will react in situ with at least part of an inorganic primary component comprising a silicate to produce an alkali metal silicate. Sodium hydroxide may also form sodium carbonate when exposed to ambient air containing C02, the rate of this to process increasing at higher temperatures (e.g. 400°C). The resulting sodium carbonate can react with silicates to form sodium silicate.
Preferably, the amount of binding agent is in the range of 0.1 to 50 wt.%
based on the total dry weight of the agglomerate precursor, more preferably 0.5 to 40 wt.% and more preferably 1 to 30 wt.%.
It has already been discussed above that it is preferred to have the binding agent towards the exterior of the precursor so that, during firing, the binding agent forms a molten skin. Formation of this molten skin should preferably be prior to or during activation of the blowing component, especially activation of the primary blowing agent.
Not only will this formation of a molten skin further protect blowing agent within the 2o precursor, it advantageously provides synthetic expanded microparticles of low density.
Using the spray drying method for forming the agglomerate precursor, it has been unexpectedly found that the concentration of the binding agent (as well as the blowing agents) witlun different zones of the agglomerate precursor can be controlled by appropriate selection of the solubility limits of this component. Accordingly, it is preferred that, using the spray drying method, the binding agent has a relatively high water-solubility so that it is more concentrated at the exterior of the agglomerate precursor and, hence, can form a molten skin during subsequent firing. Alkali compounds such as alkali hydroxides, or in particular compounds of sodium silicate and sodium aluminosilicate are preferred binding agents in this regard, since they are soluble 3o in water and can, therefore, migrate towards the exterior of the agglomerate precursor.
Method ofFornain.~ Syntlaetic Expanded Micropaf~ticles The precursors produced by the method described above may be used to synthesize expanded microparticles by firing at a predetermined temperature profile.

Preferably, the temperature profile during firing fuses the precursor into a melt, reduces the viscosity of the melt, seals the surface of the precursor and promotes expansive formation of gas within the melt to form bubbles. The temperature profile should also preferably maintain the melt at a temperature and time sufficient to allow gas bubbles to coalesce and form a single primary void. After foaming, the newly expanded particles are rapidly cooled, thus forming hollow glassy microsparticles.
Accordingly, the temperature profile is preferably provided by a furnace having one or more temperature zones, such as a drop tube furnace, a vortex type furnace, a fluidised bed furnace or a fuel-fired furnace, with upward or downward draft air streams. A
fuel-fired to furnace includes furnace types in which precursors are introduced directly into one or a multitude of combustion zones, to cause expansion or blowing of the particles.
This is a preferred type of furnace, since the particles benefit by direct rapid heating to high temperatures, which is desirable. The heat source may be electric or provided by burning fossil fuels, such as natural gas or fuel oil. However, the preferred method of heating is by combustion of natural gas, since this is more economical than electric heating and cleaner than burning fuel oil.
Typically, the peak firing temperature in firing step (b) is in the range of 600 to 2500°C, more preferably 800 to 2000°C, more preferably 1000 to 1500°C, and more preferably 1100 to 1400°C. However, it will be appreciated that the requisite 2o temperature profile will depend on the type of inorganic primary component and blowing component used.
Preferably, the exposure time to the peak firing temperature described above will be for a period of 0.05 to 20 seconds, more preferably 0.1 to 10 seconds.
Syyathetic Hollow Microspheres The present invention further provides a synthetic hollow microsphere obtained by the method described above. Such hollow microparticle are inexpensive to produce and may be used advantageously as a cheap alternative to harvested cenospheres.
Synthetic hollow microparticle according to the present invention typically comprise a substantially spherical wall with a closed shell (void) structure. The synthetic hollow 3o microparticle preferably have one or more of the following characteristics, which are also generally characteristics of harvested cenospheres:
(i) an aspect ratio of between about 0.8 and 1.

_22_ (ii) a void volume of between about 30 and 95%, based on the total volume of the microsphere;
(iii) a wall thickness of between about 5 and 30% of the microsphere radius;
(iv) a composition of 30 to 85 wt.% Si02, 2 to 45 wt.% (preferably 6 to 40 wt.%) A1203, up to about 30 wt.% divalent metal oxides (e.g. MgO, CaO, SrO, Ba0), 2 to 10 wt.% monovalent metal oxides (e.g. Na20, K20), and up to about 20 wt.% of other metal oxides, including metal oxides which exist in multiple oxidation states (e.g.
Ti02, Fe203 etc.);
(v) a silica to alumina ratio which is greater than about 1;
(vi) an average diameter of between 30 and 1000 microns, more preferably between 40 and 500 microns. (An average diameter of 30 microns or above is advantageous, because such particles are not considered to be respirable dusts);
(vii) an outer wall thickness of between 1 and 100 microns, preferably between and 70 microns, more preferably between 2.5 and 20 microns;
(viii) a particle density of between 0.1 and 2.0 g/cm3, more preferably between 0.2 and 1.5 g/cm3, and more preferably between 0.4 and 1.0 g/cm3; or (ix) a bulk density of less than about 1.4 g/cm3, preferably less than about 1.0 g/cm3.
Use of Synthetic Expanded Micf oparticles The synthetic expanded microparticles according to the present invention may be used in a wide variety of applications, for example, in filler applications, modifier applications, containment applications or substrate applications. The scope of applications is much greater than that of harvested cenospheres due to the low cost and consistent properties of synthetic microspheres.
Synthetic microparticles according to the present invention may be used as fillers in composite materials, where they impart properties of cost reduction, weight reduction, improved processing, performance enhancement, improved machinability and/or improved workability. More specifically, the synthetic microparticles may be used as fillers in polymers (including thermoset, thermoplastic, and inorganic geopolymers), 3o inorganic cementitious materials (including material comprising Portland cement, lime cement, alumina-based cements, plaster, phosphate-based cements, magnesia-based cements and other hydraulically settable binders), concrete systems (including precise concrete structures, tilt up concrete panels, columns, suspended concrete structures etc.), putties (e.g. for void filling and patching applications), wood composites (including particleboards, fibreboards, wood/polymer composites and other composite wood structures), clays, and ceramics. One particularly preferred use is in fibre cement building products.
The synthetic expanded microparticles may also be used as modifiers in combination with other materials. By appropriate selection of size and geometry, the microparticles may be combined with certain materials to provide unique characteristics, such as increased film thickness, improved distribution, improved flowability etc.
Typical modifier applications include light reflecting applications (e.g.
highway markers l0 and signs), industrial explosives, blast energy absorbing structures (e.g.
for absorbing the energy of bombs and explosives), paints and powder coating applications, grinding and blasting applications, earth drilling applications (e.g. cements for oil well drilling), adhesive formulations and acoustic or thermal insulating applications.
The synthetic expanded microparticles may also be used to contain and/or store 15 other materials. Typical containment applications include medical and medicinal applications (e.g. microcontainers for drugs), micro-containment for radioactive or toxic materials, and micro-containment for gases and liquids.
The synthetic expanded microparticles may also be used in to provide specific surface activities in various applications where surface reactions are used (i.e. substrate 2o applications). Surface activities may be further improved by subj ecting the microparticles to secondary treatments, such as metal or ceramic coating, acid leaching etc. Typical substrate applications include ion exchange applications (for removing contaminants from a fluid), catalytic applications (in which the surface of the microparticle is treated to serve as a catalyst in synthetic, conversion or decomposition 25 reactions), filtration (where contaminants are removed from gas or liquid streams), conductive fillers or RF shielding fillers for polymer composites, and medical imaging.
Brief Description of the Drawings The present invention will now be described, by way of example only, with reference to the following drawings in which:
3o Figure 1 is a phase equilibrium diagram for binary system Na20-Si02, the composition being expressed as a weight percentage of Si02;

Figure 2 is a TGA plot of three preferred blowing agents, sugar, carbon black and silicon carbide, showing sequential activation temperatures of sugar to be the lowest and carbide being the highest;
Figures 3 to 8 are scanning electron micrographs of synthetic hollow microspheres obtained from Example 1;
Figures 9 to 14 are scanning electron micrographs of synthetic hollow microspheres obtained from Example 2;
Figures 15 to 17 are scanning electron micrographs of synthetic hollow microspheres obtained from Example 3; and to Figures 18 to 19 are scanning electron micorgraphs of synthetic hollow microspheres obtained from Example 4;
Figure 20 is a scanning electron micorgraphs of synthetic hollow microspheres obtained from Example 5.
Detailed Description of Preferred Embodiments This example illustrates a method to make expanded micro-inclusions from formulations consisting of basalt and sodium hydroxide.
The formulations were prepared by mixing ground basalt with solid sodium 2o hydroxide and water. Various mixtures of blowing agents with control agents including silicon carbide, sugar, carbon black and coal were added either in combination or isolation. The formulations are shown in Table 1. The composition of the basalt is given in Table 2.
Formulation lA
This formulation illustrates a method to make expanded micro-inclusions from a formulation consisting of basalt, sodium hydroxide and sugar as the blowing agent.
A sample was prepared by mixing 92 grams of basalt; ground to a dso particle size of about 2 microns, with 5 grams of solid sodium hydroxide (flakes), 3 grams of commercial sugar and 23mL of water. The formulation is shown in Table 1.
3o Formulation 1B
This formulation illustrates a method to make expanded micro-inclusions from a formulation consisting of basalt, sodium hydroxide and carbon black as the blowing agent.

A sample was prepared by mixing 94 grams of basalt; ground to a d5o particle size of about 2 microns, with 5 grams of solid sodium hydroxide (flakes), 1 gram of a commercial grade carbon black and 38mL of water. The formulation is shown in Table 1.
Formulation 1 C
This formulation illustrates a method to make expanded micro-inclusions from a formulation consisting of basalt, sodium hydroxide and silicon carbide as the blowing agent.
A sample was prepared by mixing 94.5 grams of basalt; ground to a dso paxticle to size of about 1 micron, with 5 grams of solid sodium hydroxide (flakes), 0.5 grams of a commercial grade silicon carbide and 38mL ofwater. The formulation is shown in Table 1.
Formulation 1D
This formulation illustrates a method to make expanded micro-inclusions from a formulation consisting of basalt, sodium hydroxide, silicon carbide as the primary blowing agent and coal as the control agent or secondary blowing agent.
A sample was prepared by mixing 93.5 grams of basalt, 0.5 grams of a commercial grade silicon carbide and 1 gram of a commercial grade coal; the resulting blend being co-ground to a dsa particle size of about 1 micron. This blend was then 2o mixed with 5 grams of solid sodium hydroxide (flakes) and 38mL of water.
The formulation is shoran in Table 1.
Formulation lE
This formulation illustrates a method to make expanded micro-inclusions from a formulation consisting of basalt, sodium hydroxide, silicon carbide as the primary blowing agent and sugar as the control agent or secondary blowing agent.
A sample was prepared by mixing 92 grams of basalt; ground to a dso particle size of about 1 micron, with 5 grams of solid sodium hydroxide (flakes), 0.5 grams of a commercial grade silicon carbide, 2.5 grams of a commercial sugar and 37mL of water.
The formulation is shown in Table 1.
3o Formulation 1F
This formulation illustrates a method to make expanded micro-inclusions from a formulation consisting of basalt, sodium hydroxide, carbon black as the primary blowing agent and sugar as the control agent or secondary blowing agent.

A sample was prepared by mixing 91.4 grams of basalt; ground to a dso particle size of about 2 microns, with 4.8 grams of solid sodium hydroxide (flakes), 0.8 grams of a commercial grade carbon black, 3 grams of a commercial sugar and 38mL of water.
The formulation is shown in Table 1.
Each mixture was blended into homogeneous slurry, poured into a flat dish and allowed to solidify at room temperature for approximately 5 minutes. The resulting product was fiuther dried at about 50 degrees Celsius for about 20 hours, after wluch it was ground and sieved to obtain powders within a size range of 106 to 180 microns. In the next step, the powders were fed into a vertical heated tube furnace at an approximate l0 feed rate of 0.14 g/min. The constant temperature zone of the furnace could be adjusted to provide residence times from less than one second to approximately several seconds at the peak firing temperatures. The foamed micro-inclusions were collected on a funnel shaped collecting device covered with a fine mesh screen positioned at the bottom portion of the furnace. A mild suction was applied to the end of funnel to aid in 15 collecting the micro-inclusions. The products were characterized for particle density (e.g. apparent density), and microscopic examination by SEM. The results are summarized in Table 3.
Figures 3 to 9 show SEM examinations of the products obtained from formulations lA
to 1F respectively.

_27_ Table 1. Formulations (grams) lA to 1F
FormulationBasaltSodium Blowing AgentControl AgentWater No. Hydroxide (mL) lA 92.0 5.0 3.0 Sugar - 23 1B 94.0 5.0 1.0 Carbon - 38 Black 1C 94.5 5.0 0.5 SiC - 38 1D 93.5 5.0 0.5 SiC 1.0 powdered38 coal lE 92.0 5.0 0.5 SiC 2.5 Sugar 37 1F 91.4 4.8 . 0.8 Carbon 3.0 Sugar 38 Black Table 2. Composition of Basalt Si02 A1a03 Fe203 Ca0 Mg0 S03 NazO Ka0 Ti02 Mn203 P205 Total 46.1 15.8 11.4 9.5 9.6 0.0 2.8 1.5 2.4 0.25 0.59 99.94 Table 3. Result Summary FormulationTemperatureResidence Apparent No. (degree time density C) (second) (g/cm3) lA 1300 0.6-1.1 1.28 1B 1300 0.6-1.1 1.13 1C 1250 0.6-1.1 1.13 1D 1300 0.6-1.1 0.82 lE 1300 0.6-1.1 0.85 1F 1300 0.6-1.1 1.21 Following conclusions can be drawn from Example 1.
1- SiC is a more effective primary blowing agent than carbon and sugar to lower io the particle density. Note that the net carbon content of SiC (30 wt%
carbon) is less than equivalent mass of carbon in carbon (100 wt %), and sugar (40 wt% carbon).
2- Use of SiC with one or more control agents is more effective in lowering the particle density compared to any single blowing agent used in this example.
3- The combination of any single blowing agent with a control agent can be optimized to strongly influence the product's particle density, i.e. all SiC
combinations are more effective to lower the particle density as compared to carbon-sugar combination.

This example illustrates a method to make expanded micro-inclusions from a formulation consisting of various silicate compounds, sodium hydroxide and multi-blowing agents.
Expanded micro-inclusions were prepared using blends of a soda lime waste glass and various silicate materials. These blends also include mixtures of a primary blowing agent with control agents of silicon carbide with control agents, sugar, and/or carbon black. The formulations are shown in Table 4. The composition of the waste glass used in this work is given in Table 5.
l0 Formulation 2A
This formulation illustrates a method to make expanded micro-inclusions from a formulation consisting of glass, sodium hydroxide, with silicon carbide as the blowing agent and carbon black as the control agent.
A sample was prepared by mixing 95.6 grams of glass; ground to a dso particle 15 size of about 1 micron, with 3 grams of solid sodium hydroxide (flakes), 0.4 grams of a commercial grade silicon carbide, 1 gram of a commercial grade carbon black and 58mL
of water. The formulation is shown in Table 4.
Formulation 2B
This formulation illustrates a method to make expanded micro-inclusions from a 2o formulation consisting of glass, fly ash, sodium hydroxide, with silicon carbide as the blowing agent and carbon black as the control agent.
A sample was prepared by mixing 65.5 grams of glass and 28.1 grams of fly ash;
the mixture being co-ground to a dso particle size of about 2 microns. The glass/fly ash blend was mixed with 5 grams of solid sodium hydroxide (flakes), 0.4 grams of a 25 commercial grade silicon carbide, 1 gram of a commercial grade carbon black and 42mL
of water. The formulation is shown in Table 4. The composition of the fly ash is given in Table 5.
Formulation 2C
This formulation illustrates a method to make expanded micro-inclusions from a 3o formulation consisting of glass, basalt, sodium hydroxide, with silicon carbide as the blowing agent and carbon black as the control agent.
A sample was prepared by mixing 46.8 grams of glass and 46.8 grams of basalt;
the mixture being co-ground to a dso particle size of about 2 microns. The glass/basalt blend was mixed with 5 grams of solid sodium hydroxide (flakes), 0.4 grams of a commercial grade silicon carbide, 1 gram of a commercial grade carbon black and 37mL
of water. The formulation is shown in Table 4. The composition of the basalt is given in Table 5.
Formulation 2D
This formulation illustrates a method to make expanded micro-inclusions from a formulation consisting of glass, volcanic ash, sodium hydroxide, with silicon carbide as the blowing agent and carbon black as the control agent.
A sample was prepared by mixing 46.8 grams of glass and 46.8 grams of l0 volcanic ash; the mixture being co-ground to a d5o particle size of about 2 microns. The glass/volcanic ash blend was mixed with 5 grams of solid sodium hydroxide (flakes), 0.4 grams of a commercial grade silicon carbide, 1 gram of a commercial grade carbon black and SOmL of water. The formulation is shown in Table 4. The composition of the volcanic ash is given in Table 5.
Formulation 2E
This formulation illustrates a method to make expanded micro-inclusions from a formulation consisting of glass, andesite, sodium hydroxide, with silicon carbide as the primary blowing agent and sugar as the control agent.
A sample was prepared by mixing 47.1 grams of glass and 47.1 grams of 2o andesite; the mixture being co-ground to a dso particle size of about 2 microns. The glasslandesite blend was mixed with 3 grams of solid sodium hydroxide (flakes), 0.4 grams of a commercial grade silicon carbide, 2.5 grams of sugar and SOmL of water. The formulation is shown in Table 4. The composition of the andesite is given in Table 5.
Formulation 2F
This formulation illustrates a method to make expanded micro-inclusions from a formulation consisting of glass, andesite, sodium hydroxide, with silicon carbide as the blowing agent and carbon black as the control agent.
A sample was prepared by mixing 47.8 grams of glass and 47.8 grams of andesite; the mixture being co-ground to a dso particle size of about 1 micron. The 3o glass/andesite blend was mixed with 3 grams of solid sodium hydroxide (flakes), 0.4 grams of a commercial grade silicon carbide, 1 gram of a commercial grade carbon black and 43mL of water. The formulation is shown in Table 4.

Each mixture was blended into homogeneous slurry, poured into a flat dish and allowed to solidify at room temperature for approximately 5 minutes. The resulting product was further dried at about 50 degrees Celsius for about 20 hours, after which it was ground and sieved to obtain powders within a size range of 106 to 180 microns. In the next step, the powders were fed into a vertical heated tube furnace at an approximate feed rate of 0.14 g/min. The constant temperature zone of the furnace could be adjusted to provide residence times from less than one second to approximately several seconds at the peak firing temperatures. The foamed micro-inclusions were collected on a funnel shaped collecting device covered with a fine mesh screen positioned at the bottom 1o portion of the furnace. A mild suction was applied to the end of funnel to aid in collecting the micro-inclusions. The products were characterized for particle density (e.g. apparent density), and microscopic examination by SEM.
The results are summarized in Table 6.
Figures 10 to 16 show SEM cross sectional views for each of samples 2A to 2F.
Table 4. Formulations (grams) 2A to 2F
Formulation Waste Additional Sodium Blowing Water No. Glass Component Hydroxide Agent Control Agent (mL) 2A 95.6 - 3.0 0.4 SiC 1.0 Carbon 58 Black 2B 65.5 28.1 fly 5.0 0.4 SiC 1.0 Carbon 42 ash Black 2C 46.8 46.8 basalt 5.0 0.4 SiC 1.0 Carbon 37 Black 2D 46.8 46.8 5.0 0.4 SiC 1.0 Carbon 50 volcanic Black ash 2E 47.1 47.1 andesite3.0 0.4 SiC 2.5 Sugar 42 2F 47.8 47.8 andesite3.0 ' 0.4 SiC 1.0 Carbon 43 Black Table 5.
Chemical Compositions Si02A120 Fe203 Ca0 Mg S03 Na2 KZO Ti02 Mn2O3 PZOs Total O O

Glass 74.72.0 0.9 11.1 0.6 0.0 10.0 0.5 0.06 0.06 0.02 99.94 Fly 52.720.2 13.2 7.6 2.5 0.4 0.4 1.3 1.3 0.16 0.08 99.84 Ash Volcani76.412.4 2.1 0.9 0.3 0.0 2.1 5.5 0.15 0.08 0.03 99.96 c Ash Andesit67.815.2 4.6 2.1 0.6 0.0 2.7 4.9 0.7 0.9 0.28 99.78 a Table 6. Result Summary FormulationTemperatureResidenceApparent No. (degree time density C) (second) (g/cm3) 2A 1200 0.6-1.1 0.98 2B 1300 0.6-1.1 l.ll 2C 1200 0.6-1.1 0.93 2D 1200 0.6-1.1 0.94 2E 1300 0.6-1.1 0.93 2F 1300 0.6-1.1 0.77 The following conclusions can be drawn from Example 2.
1- The combination of blowing agent with control agent i.e. silicon carbide-carbon and silicon carbide-sugar is very effective in production of expanded micro-inclusions.
2- Waste glass is an economical and suitable addition to various silicate mixtures.
3- Silicate raw materials, appropriate for production of expanded micro-inclusions according to the method of present invention can be selected from a wide range of waste byproducts, minerals, chemicals, and rocks.
Example 3 This example illustrates a method to make expanded micro-inclusions from formulations consisting of various quantities of volcanic ash, sodium hydroxide, mixtures of blowing and control agents and other minor additives.
Formulation 3A
A sample was prepared by mixing 78.2 grams of volcanic ash; ground to a d5o 2o particle size of about 3 microns, with 20 grams of solid sodium hydroxide (flakes), 0.8 grams of a commercial grade silicon carbide as the primary blowing agent, 1 gram of a commercial grade carbon black as the control agent and 43mL of water.

Formulation 3B and 3C
Samples were prepared using a blend of volcanic ash and iron (III) oxide that was co-ground to a dso particle size of approximately 1 micron. The formulations are shown in Table 7. The composition of the volcanic ash is given in Table 5. The mixture was blended into homogeneous slurry, poured into a flat dish and allowed to solidify at room temperature for approximately 5 minutes. The resulting product was further dried at about 50 degrees Celsius for about 20 hours, after which it was ground and sieved to obtain powders within a size range of 106 to 180 microns. In the next step, the powders were fed into a vertical heated tube furnace at an approximate feed rate of 0.14 g/min.
The constant temperature zone of the furnace could be adjusted to provide residence times from less than one second to approximately several seconds at the peak firing temperatures. The foamed micro-inclusions were collected on a funnel shaped collecting device covered with a fine mesh screen positioned at the bottom portion of the furnace.
A mild suction was applied to the end of funnel to aid in collecting the micro-inclusions.
The products were characterized for particle density (e.g. apparent density), and microscopic examination by SEM.
The results are summarized in Table 8.
Figures 17 to 20 show two cross sections per sample, of the products of Formulations 3A to 3C respectively.
Table 7. Formulations (grams) 3A to 3C
FormulationVolcanic Sodium Blowing Control Iron Water No. Ash Hydroxide Agents Agents (III) (mL) Oxide 3A 78.2 20.0 0.8 SiC 1.0 Carbon 43 Black 3B 76.6 19.6 0.8 1.0 Carbon2.0 43 Black 3C 86.2 9.8 0.8 1.0 Carbon2.2 43 Blaclc Table 8. Result Summary FormulationTemperatureResidenceApparent No. (degree time density C) (second) (glcm3) 3A 1200 0.6-1.1 0.71 3B 1200 0.6-1.1 0.60 3C" 1200 0.6-1.1 0_59 Following conclusions can be drawn from Example 3.
1- Combination of silicon carbide as primary blowing agent and carbon black as control agent is very effective in expanding volcanic ash into very light rounded product.
2- As sodium concentration is increased in the formulation, the product roundness approaches near spherical shape. Sodium oxide is a powerful fluxing agent for silicate glasses, e.g. viscosity reducer. Therefore, less viscous formulations tend to form spherical expanded particles rather than only rounded micro-particles, primarily because of lower surface tension at 1o the firing temperature.
Example 4 This example illustrates a method to make expanded micro-inclusions from formulations consisting of fly ash, sodium hydroxide, and blowing control agents.
Formulation 4A
15 A sample was prepared by mixing 79 grams of a type F fly ash; ground to a dso particle size of about 4 microns, with 19 grams of solid sodium hydroxide (flakes), 1 gram of a commercial grade silicon carbide as the primary blowing agent, 1 gram of a commercial grade carbon black as the control agent and 42mL of water.
Formulation 4B
2o A sample was made by mixing 68.7 grams of a type F fly ash similar to the one used in formulation 4A, with 29.5 grams of solid sodium hydroxide, as shown in Table 9. The composition of the fly ash is given in Table 5.
The mixture was blended into homogeneous slurry, poured into a flat dish and allowed to solidify at room temperature for approximately 5 minutes. The resulting 25 product was further dried at about 50 degrees Celsius for about 20 hours, after which it was ground and sieved to obtain powders within a size range of 106 to 180 microns. In the next step, the powders were fed into a vertical heated tube furnace at an approximate feed rate of 0.14 g/min. The constant temperature zone of the furnace could be adjusted to provide residence times from less than one second to approximately several seconds 3o at the peak firing temperatures. The foamed micro-inclusions were collected on a funnel shaped collecting device covered with a fine mesh screen positioned at the bottom portion of the fiunace. A mild suction was applied to the end of funnel to aid in collecting the micro-inclusions. The products were characterized for particle density (e.g. apparent density), and microscopic examination by SEM.
The results are summarized in Table 10.
Figures 21 and 22 show two cross sections per sample, of the products of Formulations 4A and 4B respectively.
Table 9. Formulations (grams) 4A and 4B
Formulation Fly Sodium Blowing Control Agent Water (mL) ash No. Hydroxide Agent 4A 79.0 19.0 1.0 SiC 1.0 Carbon Black 42.0 4B 68.7 29.5 0.8 SiC 1.0 Carbon Black 43.0 Table 10. Result Summary FormulationTemperatureResidenceApparent No. (degree time density C) (second) (g/cm3) 4A 1200 0.6-1.1 0.67 4B 1200 0.6-1.1 1.03 to Following conclusions can be drawn from Example 4.
1- A combination of silicon carbide as the primary blowing agent and carbon as the control agent is very effective in producing low density micro-inclusions from a silicate waste byproduct, fly ash.
2- The concentration of fluxing compound (e.g. sodium hydroxide?) can be optimized to produce excellent spherical micro-inclusions with low particle density.
3- Higher concentration of fluxing agent beyond an optimum value, not only increases the particle density of the product, but also negatively impacts the 2o economy. Waste fly ash is much less expensive than sodium hydroxide.
Example 5 This example illustrates a method to make expanded micro-inclusions from a formulation consisting of phosphatic clay a waste byproduct from phosphate ore beneficiation, sodium hydroxide, silicon carbide and carbon black.
Formulation SA
A sample was prepared by mixing 88.4 grams of phosphatic clay; ground to a dso particle size of 0.6 microns, with 9.8 grams of solid sodium hydroxide (flakes), 0.8 grams of a commercial grade silicon carbide, 1.0 grams of a commercial grade carbon black and 85mL of water. The composition of the phosphatic clay is given in Table 11.
The mixture was blended into homogeneous slurry, poured into a flat dish and allowed to solidify at room temperature for approximately 5 minutes. The resulting product was further dried at about 50 degrees Celsius for about 20 hours, after which it was ground and sieved to obtain powders within a size range of 106 to 180 microns. In the next step, the powders were fed into a vertical heated tube furnace at an approximate feed rate of 0.14 g/min. The constant temperature zone of the furnace could be adjusted to provide residence times from less than one second to approximately several seconds at the peak firing temperatures. The foamed micro-inclusions were collected on a funnel shaped 1o collecting device covered with a fine mesh screen positioned at the bottom portion of the furnace. A mild suction was applied to the end of funnel to aid in collecting the micro-inclusions. The products were characterized for particle density (e.g.
apparent density), and microscopic examination by SEM.
The results are summarized in Table 12.
Figures 35 and 36 show the cross section of the product.
Table 11. Chemical Composition of Phosphatic Clay Si02 A1203 Fe203 Ca0 Mg0 S03 Na20 K20 TiOa Mn203 P205 Total 36.5 17.8 2.7 20.8 3.4 0.33 0.29 0.88 0.57 0.05 16.7 100.0 Table 12. Result Summary Temperature Residence Apparent density (degree C) time (second) (g/cm3) 1300 0.8-1.5 0.92 2o Following conclusions can be drawn from Example 5.
1- Multi-blowing agent combination of silicon carbide and carbon has been effectively used to produce low density micro-inclusions from a waste clay byproduct.
2- The P205-Ca0 combined concentration is more than 33% of the total wt% of the product. The combination can potentially form an amorphous apatite phase in the product.
Apatite containing product may exhibit useful bioactive reactions in medical applications.

It will be understood that the present invention may be embodied in other forms without departing from the spirit or scope of the inventive idea.

Claims (40)

1. A method of producing a low density material comprising providing a precursor by forming an aqueous mixture of inorganic primary component and more than one blowing agent, wherein each blowing agent is selected to operate at a different temperature range, wherein the precursor has an alkali metal oxide content of less than 10 wt. %
based on the total dry weight of the precursor;
drying the mixture and firing the precursor to activate each blowing agent to expand the precursor and form a low density material wherein activation of each blowing agent is controlled and this activation controls expansion of the precursor such that each blowing agent is activated within its own predetermined optimal temperature range.

2. The method of claim 1 wherein the low density material is a microparticle with a diameter of up to about 1.000 microns.

3. The method of claim I or claim 2 wherein the more than one blowing agent is activated within a temperature range in which the inorganic primary component has melted and is within an optimal viscosity range.

4. The method according to any one of claims 1-3 wherein the more than one blowing agent is controlled by a control agent.

5. The method according to any one of claims 1-4 wherein the more than one blowing agent is provided as a primary blowing agent and a control agent, and the control agent is provided as a secondary blowing agent.

6. The method according to any one of claims 1-5 wherein the more than one blowing agent includes a primary blowing agent having a first activation temperature and a secondary blowing agent having a second activation temperature which is less than the first activation temperature.

7. The method according to any one of claims 1-6, wherein the more than one blowing agent includes a primary blowing agent is selected from the group consisting of powdered coal, carbon black, activated carbon, graphite, carbonaceous polymeric organics, oils, carbohydrates, PVA, carbonates, carbides, sulfates, sulfides, nitrides, nitrates, amines, polyols, glycols, glycerine, and combinations thereof.

8. The method according to any one of claims 1-7, wherein the more than one blowing agent includes a secondary blowing agent selected from the group consisting of powdered coal, carbon black, activated carbon, graphite, carbonaceous polymeric organics, oils, carbohydrates, PVA, carbonates, carbides, sulfates, sulfides, nitrides, nitrates, amines, polyols, glycols, glycerine, and combinations thereof.

9. The method according to any one of claims 1-8, wherein the precursor further comprises a tertiary blowing agent having a third activation temperature, wherein the third activation temperature is less than the first activation temperature.

10. The method according to any one of claims 1-9, wherein the more than one blowing agent includes a tertiary blowing agent selected from the group consisting of powdered coal, carbon black, activated carbon, graphite, carbonaceous polymeric organics, oils, carbohydrates, PVA, carbonates, sulfates, sulfides, nitrates, amines, polyols, glycols, glycerine, and combinations thereof.

11. The method according to any one of claims 1-10, wherein firing of the precursor is conducted under such conditions as to control activation of the blowing agent.

12. The method according to any one of claims 1-11 wherein firing of the precursor is conducted in an oxygen deficient environment.

13. The method according to claim 12 wherein firing of the precursor is conducted in a fuel rich and less oxidising environment.

14. The method according to any one of claims 1-13, wherein activation of the more than one blowing agent is controlled by appropriate dosing with O2 depleting or O2 enriching gases during firing of the precursor.

15. The method according to any one of claims 1-14 wherein the precursor is formed with a predetermined distribution of blowing agent there through, said distribution providing a controlled activation of the blowing agent during firing of the precursor.

16. The method according to any one of claims 1-15, wherein the drying step is performed using a spray dryer having an aqueous slurry feed, wherein the spray dryer has an inlet temperature in the range of about 300 to 600°C.

17. The method of any one of claims 1-16, wherein the amount of inorganic primary component is at least 50 wt.%, based on the total dry weight of the agglomerate precursor.

18. The method of any one of claims 1-17, wherein the amount of blowing component is in the range of 0.05 to 10 wt.%, based on the total dry weight of the precursor.

19. The method of any one of claims 1-18 wherein the ratio of inorganic primary component to blowing component is in the range of 1000:1 to 10:1.

20. The method of any one of claims 1-19, wherein the mixture is dried such that the water content of the precursor is less than about 14 wt.%.

21. The method of any one of claims 1-20, wherein the resultant agglomerate precursors have an average agglomerate particle size in the range of 10 to 1000 microns.

22. The method of any one of claims 1-21, wherein the inorganic primary component comprises at least one material selected from inorganic oxides, non-oxides, salts or combinations thereof, or comprises at least one material selected from industrial by products, residential by-products, minerals, rocks, clays, technical grade chemicals and combinations thereof.

23. The method of any one of claims 1-22, wherein the inorganic primary component comprises at least one silicate material, selected from fly ash, bottom ash, blast-furnace slag, paper ash, basaltic rock, andesitic rock, feldspars, aluminosilicate clays, bauxite, volcanic ash, volcanic rocks, volcanic glasses, geopolymers, or combinations thereof.

24. The method of any one of - claims 1-23, wherein the inorganic primary component has an average primary particle size in the range of 0.01 to 100 microns.

25. The method according to any one of claims 5 to 24, wherein the primary blowing agent is relatively less water-soluble than the secondary blowing agent.

26. The method of any one of claims 1-25, wherein the blowing agent has an average particle size in the range of 0.01 to 10 microns.

27. The method of any one of claims 1-26, further comprising mixing a binding agent with the inorganic primary component and the blowing agent wherein the binding agent is selected from alkali metal silicates, alkali metal aluminosilicates, alkali metal borates, alkali or alkaline earth metal carbonates, alkali or alkaline earth metal nitrates, alkali or alkaline earth metal nitrites, boric acid, alkali or alkaline earth metal sulfates, alkali or alkaline earth metal phosphates, alkali or alkaline earth metal hydroxides, carbohydrates, colloidal silica, ultrafine fly ash, Type C fly ash, Type F fly ash, inorganic silicate cements, Portland cement, alumina cement, lime-based cement, phosphate-based cement, organic polymers and combinations thereof.

28. The method of claim 27, wherein the binding agent has a melting point which is lower than the melting point of the resultant agglomerate precursor as a whole.

29. The method of any one of claims 27 to 28, wherein the binding agent has a melting point in the range of 700 to 1000°C.

30. The method of claim 27 or 29, wherein the binding agent is a silicate.

31. The method of claim 27 or 30, wherein the binding agent is an alkali metal silicate generated by in situ reaction of an alkali metal hydroxide and an silicate primary component.

32. The method of any one of claims 27 to 31, wherein the amount of binding agent is in the range of 0.1 to 50 wt.%, based on the total dry weight of the precursor.

33. The method of any of claims 27 to 32, wherein the binding agent is relatively more water-soluble than the primary blowing agent.

34. The method of any one of claims 1-33, wherein the primary component, the blowing component and, optionally, the binding agent are co-ground together.

35. A method of forming a precursor for a low density material comprising the steps o f: providing an inorganic primary component; forming an aqueous mixture of the inorganic primary component, a blowing agent and a control agent, and drying the mixture to provide an expandable precursor for forming a low density material wherein said blowing agent and control agent are selected to control activation of the blowing agent such that the blowing agent is activated within a predetermined optimal temperature range different than the temperature range of the control agent, wherein the precursor prior to expansion has an alkali metal oxide content of less than 10 wt. % based on the total dry weight of the precursor.

36. A method of forming a precursor for a low density material comprising the steps of. providing an inorganic primary component; forming an aqueous mixture of the inorganic primary component and a blowing agent; and drying the mixture to provide an expandable precursor for forming a low density material wherein said blowing agent is selected and/or distributed in the precursor to control activation of the blowing agent upon firing of the precursor such that the blowing agent is activated within a predetermined optimal temperature range.

37. A method of controlling activation of the blowing agent in an inorganic mixture to produce expanded micro particles, said method comprising:
providing more than one blowing agent each of which is activated under predetermined and different conditions to release a blowing gas and produce expanded micro particles, wherein the expanded micro particles before expansion have an alkali metal oxide content of less than 10 wt. % based on the total dry weight of the precursor; and controlling such conditions whereby said activation takes place within a predetermined optimal viscosity range of the inorganic mixture.

38. A method of producing a low density material comprising:
providing a precursor by forming an aqueous mixture of inorganic primary component and more than one blowing agent, wherein the precursor has an alkali metal oxide content of less than 10 wt. % based on the total dry weight of the precursor, wherein the blowing agents are selected to be activated within predetermined and different optimal temperature ranges;
drying the mixture; and firing the precursor to activate each blowing agent for controlled expansion of the precursor, thereby forming a low density material.

39. A low density material when produced by the method according to any one of claims 1 to 34 , or 38.

40. A precursor for low density material when produced by the method according to any one of claims 35 to 36.