PROCESS FOR PRODUCING A FOAM CERAMIC

Abstract

The present invention relates to a process for producing a foam ceramic comprising the steps: producing an aqueous suspension of a first mineral raw material; foaming the suspension with air while adding a foaming agent and a binder to form a light foam; mixing the light foam with a powder or slip of a second ceramic raw material to form a heavy foam; pouring the heavy foam into a mold; drying the molded heavy foam in the mold to form a solid foam; and firing the solid foam in the mold to form the foam ceramic.

Claims

1. A process for producing a foam ceramic comprising the steps: producing an aqueous suspension of a first mineral raw material; foaming the suspension with air while adding a foaming agent and a binder to form a light foam; mixing the light foam with a powder or slip of a second ceramic raw material to form a heavy foam; pouring the heavy foam into a mold; drying the molded heavy foam in the mold to form a solid foam; and firing the solid foam in the mold to form the foam ceramic.

2. The process according to claim 1, wherein the mold at least partly burns off in the step of firing.

3. The process according to claim 1, wherein the mold is made of bagasse or polylactic acid.

4. The process according to claim 1, wherein linear mixers are used for foaming and/or for mixing.

5. The process according to claim 1, wherein the solid foam is not manipulated between the steps of drying and firing.

6. The process according to claim 1, wherein the first mineral raw material is a two-component powder made of muscovite mica and quartz.

7. The process according to claim 1, wherein the second mineral raw material is a two-component powder made of muscovite mica and quartz.

8. The process according to claim 1, wherein both the first and the second mineral raw materials are a powder made of synthetic sintered mullite.

9. The process according to claim 1, wherein in the step of producing, the suspension is wet ground with milling balls for several hours.

10. The process according to claim 1, wherein a non-ionic surfactant or a protein is used as the foaming agent.

11. The process according to claim 1, wherein the binder comprises one or more of cellulose fibers, cellulose derivatives, amylose, amylopectin, and cellobiose.

12. The process according to claim 1, wherein the light foam is mixed with slip, and further wherein the slip includes a liquefier.

13. The process according to claim 12, wherein the liquefier is based on alkali huminate and/or alkali silicate.

14. The process according to claim 1, wherein the drying is done at a temperature between 30° and 200° C.

15. The process according to claim 1, wherein the firing is done at a temperature between 400° and 2,000° C.

16. The process according to claim 6, wherein the first mineral raw material has a d50 particle size of maximum 10 μm.

17. The process according to claim 6, wherein the first mineral raw material has a d50 particle size of about 3 μm.

18. The process according to claim 7, wherein the second mineral raw material has a d50 particle size of maximum 25 μm.

19. The process according to claim 7, wherein the second mineral raw material has a d50 particle size of about 4 μm.

20. The process according to claim 8, wherein said powder has a d50 particle size of maximum 30-40 μm.

21. The process according to claim 8, wherein said powder has a d50 particle size of about 3-5 μm.

Description

[0027] The invention is explained in detail below on the basis of several sample embodiments that are shown in the single attached drawing and are described further below.

[0028] FIG. 1 shows the inventive process and various variant embodiments of it in a schematic flow chart.

[0029] FIG. 1 shows the production of an aqueous suspension of a first mineral raw material in step 1 of a process branch A. Optionally, the suspension is wet ground with milling balls for several hours, preferably at least 6 h, to break up agglomerations and homogenize it, as is symbolized by the area of step 1 surrounded by the dashed line in FIG. 1.

[0030] In step 2, a foaming agent and a binder are added to the suspension, and it is foamed with air to 5 to 25 times its volume to form a light foam, so that the density of the light foam is about 20 g/L to 300 g/L. The foaming can be done, e.g., with a basket agitator or in a linear mixer.

[0031] Foaming agents that can be used are surface-active substances from the classes of the anionic and non-ionic surfactants or plant, animal, or artificial proteins, such as, e.g., ethoxylates, alkyl glycosides, aminoxides, sodium olefin, fatty alcohols, sodium lauryl sulfate, or ammonium lauryl sulfate. Binders that can be used in addition to fire cement also include calcium hydrate, plaster, various forms of silica such as micro or nanosilica, and construction chemistry additives such as starch, cellulose fibers, cellulose derivates or cellobiose, cellulose fibers, cellulose derivatives, amylose, amylopectin, or cellobiose having turned out to be especially suitable. If desired, it is also possible to use two or more different foaming agents and/or binders as well as dehydrating agents in the way know to the person skilled in the art.

[0032] In a process branch B that is parallel to, i.e., upstream of, coordinate with, or downstream of process branch A, a powder of a second ceramic raw material is prepared and/or a slip of this raw material is produced in a step 3.

[0033] Examples of suitable first or second mineral raw materials are kaolin, metakaolin, mica, feldspar, clay, porcelain, fireclay, silicon dioxide, andalusite and kyanite, bauxite, mullite (fused and/or sintered mullite), aluminum oxide (fused corundum and/or sintered alumina), aluminum zirconium silicate or zircon mullite, zircon or zircon silicate, zirconium oxide or baddeleyite or silicon carbide in various grain sizes, and mixtures of them. Furthermore, already fired, ground ceramics or foam ceramics can be recycled.

[0034] In a variant embodiment, the first and second mineral raw materials are both a two-component powder made of muscovite mica and quartz, which, when used as first mineral raw material, has a d50 particle size of maximum 10 μm, preferably about 3 μm, and when used as the second mineral raw material has a d50 particle size of maximum 25 μm, preferably about 4 μm. The d50 particle size is the size that 50% of the particles of a powdered raw material fall below. Such mineral raw materials are available, for example, under the trade names Aspolit® F30 (d50=3 μm) or Aspolit® F40 (d50=4 μm) from the company Aspanger Bergbau and Mineralwerke GmbH & Co KG in Aspang, Austria. According to the manufacturer's data, Aspolit® has the following chemical characteristics: 69.0% SiO.sub.2, 14.0% Al.sub.2O.sub.3, 5.5% K.sub.2O, 2.0% CaO, 2.0% Fe.sub.2O.sub.3, 2.0% MgO, 0.4% TiO.sub.2, 0.2% P.sub.2O.sub.5, 0.03% MnO, 4.87% loss on ignition.

[0035] In a variant that is alternative to that, the first and second mineral raw materials are both a synthetic sintered mullite that, e.g., has a d50 particle size of maximum 30-40 μm, preferably about 3-5 μm. Such sintered mullites are available, for example, under the names Symulox® M72 (particle size K0 C) of the company Nabaltec AG in Schwandorf, Germany. According to the manufacturer's data, Symulox® M72 has the following chemical characteristics: 72% Al.sub.2O.sub.3, 26% SiO.sub.2, 0.3% Fe.sub.2O.sub.3, 0.2% TiO.sub.2, 0.05% CaO, 0.1% MgO, 0.2% Na.sub.2O, 0.6% K.sub.2O.

[0036] The first mineral raw material can differ from the second in its composition, on the one hand, and in its particle size, on the other hand; however it is also possible for them to have the same composition and/or particle size, as is shown by the mentioned variant embodiments.

[0037] To reduce the input of water when the slip is made, it is possible to add a liquefier, e.g., based on an alkali huminate and/or an alkali silicate. One that has proved effective is Dolaflux® SP 11 of the company Zschimmer & Schwarz GmbH & Co KG Chemische Fabriken in Lahnstein, Germany.

[0038] In a step 4 according to FIG. 1, the light foam produced in step 2 is mixed (blended) with the powder prepared and/or the slip produced in step 3 to form a heavy foam with a density between 50 g/L and 1,500 g/L, for example with the help of a double-shaft basket mixer or another linear mixer, and after that poured into a mold in a step 5. To avoid the uptake of water and thus also fine particles from the heavy foam, the mold the mold can be hydrophobic, e.g., lined with a polyethylene film.

[0039] In the mold, the solid-loaded liquid heavy foam is dried, in a step 6, to form a solid foam, which is fired, preferably while it is still in the mold, i.e., without further manipulation, to form a foam ceramic (step 7).

[0040] The drying of step 6 is done, for example, at a temperature between 30° and 200° C., preferably between 40° and 95° C., especially preferably at about 50° C., and the firing of step 7 is done at a temperature between 400° and 2,000° C., preferably between 500° and 1,650° C., especially preferably at about 960° C.

[0041] In step 6 of the drying it is possible to use a hot-air drier, a radio dryer, or a microwave dryer. Depending on the shape and nature of the mold, the humidity of the ambient air, and the moisture in the heavy foam, its components, the type of the dryer and the air circulation in it, the solid foam is dried in it for several hours, typically 3 to 6 hours, until it has a residual moisture of less than 5 weight percent, preferably less than 1 weight percent. As is known to the person skilled in the art, the temperature can be changed during the process, e.g., it can be increased in steps, as is also the case during firing 7. The firing process (step 7) usually lasts less than 6 hours, typically about 1 to 3 hours.

[0042] The mold used can be heat-resistant, e.g., a stainless steel wire net or a shell made of fireclay or refractory concrete, and thus be reusable; alternatively, it can be a lost mold that burns as free of residue as possible in step 7 of the firing. Such a mold is made, for example, of a bioplastic, e.g. a cellulose-based plastic, starch, or a starch mixture, polylactic acid (PLA), polyhydroxyalkanoates, or bagasse—or of hydrophobized paper or cardboard—so that it allows high vapor diffusion. Moreover, mixed variants of the molds are possible, e.g., a cardboard mold is supported by a stainless steel wire net, so that only the cardboard portion of the mold burns off, or a shell made of fireclay lined with a possibly perforated polyethylene film, so that only this film burns off.

[0043] Some examples of the process are indicated below, and the characteristics associated with the foam ceramics that are produced are given in the following Table 1.

EXAMPLE 1

[0044] ASPOLIT® F30 (d50=3 μm) was used as the first mineral raw material, which was wet ground with milling balls for 6 h, yielding a suspension that was 50 weight percent solid. The foaming agent was protein dosed as indicated by the manufacturer, and cellulose fibers were added as a binder; after foaming in a linear mixer, the light foam had a density of about 40 g/L.

[0045] A thin-member counter rotating double-shaft basket mixer was used to mix the light foam with an aqueous slip that was produced with ASPOLIT® F40 (d50=4 μm) as the second mineral raw material with the addition of Dolaflux® SP 11 as a liquefier; the resulting heavy foam had a density of 260 g/L.

[0046] The heavy foam was poured into a 100×100×40 mm.sup.3 cardboard mold lined with polyethylene, dried for 6 h at 50° C., and fired for 2 h at 960° C. in the same kiln, without manipulation.

EXAMPLE 2

[0047] In contrast to example 1, in example 2 the first raw material (once again ASPOLIT® F30) was wet ground with milling balls for 8 h and less foamed, so that the density of the light foam was about 60 g/L and the density of the heavy foam was 320 g/L. The drying was done for 5 h at 70° C. All other process parameters were as in example 1.

EXAMPLE 3

[0048] In this example, the first raw material was ASPOLIT® F40, which was wet ground with milling balls for 3 h, with a final solids content of about 45 weight percent. The foaming agent and binder used were aminoxide and cellobiose, respectively, which were dosed as indicated by the manufacturer. The light foam had a density of 60 g/L. The slip was produced with ASPOLIT® G200 (d50=18 μm), without additional liquefier. The resulting density of the heavy foam was 380 g/L. The heavy foam was poured into a bagasse mold (100×100×40 mm.sup.3), dried for 5 h at 60° C., and fired for 2 h at 1,030° C.

EXAMPLE 4

[0049] In this case, ASPOLIT® F30 was wet ground with milling balls for 12 h; the solids content was then 55 weight percent. The foaming agent and binder added were aminoxide (as indicated by the manufacturer) and 2.5 weight percent cement, respectively, and the suspension was foamed to a density of 35 g/L. The density of the heavy foam after mixing with the slip (here: with ASPOLIT® F70, d50=7 μm, and Dolaflux® SP 11 as liquefier) was 220 g/L; once again it was poured into a bagasse mold according to example 3, dried for 4 h at 50° C., and fired for 2 h at 900° C.

EXAMPLE 5

[0050] Here mullite, nano alumina, and nano-silica in the form of a powder having a specific surface of more than 50 m.sup.2/g were mixed with water in the ratio 2:1; the solids content after that was 60 weight percent. The foaming agent was protein dosed as indicated by the manufacturer, and cellulose fibers were added as a binder; the suspension was foamed to a density of 200 g/L in the linear mixer. After the powdered synthetic sintered mullite (Symulox® M72, particle size KO C with d50=3-5 μm) was sprinkled onto the heavy foam and folded in, its density was 480 g/L. The heavy foam was poured into in a PLA mold, dried for 4 h at 50° C., and fired for 2 h at 1,600° C.

[0051] The results of examples 1 through 5 are listed in the following Table 1.

TABLE-US-00001 TABLE 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Density of foam ceramic 180 220 260 150 310 [g/L] Porosity 93.3% 91.9% 90.4% 94.4% 90.3% Thermal conductivity 0.06 0.07 0.1 0.07 0.27 [W/(m .Math. K)] (ASTM at 200° C.) Cold compression 0.25 0.7 0.8 0.2 1.0 strength [MPa]

[0052] As can be seen, the foam ceramics of all examples 1 through 5 achieved a very low thermal conductivity, and thus good insulation characteristics; the respective cold compression strengths are also comparable with those of conventional low-temperature insulating materials, e.g., foamed polystyrene (such as Styropor®), or are even higher, however the foam ceramics of examples 1 through 5 are fire-resistant, and thus can be used in the high temperature range (over 600° C.)

[0053] The invention is not limited to the presented embodiments, but rather comprises all variants and modifications that fall within the scope of the associated claims.