NL8200597A - FIRE-RESISTANT OR FLAME-RESISTANT COMPOSITE CONSTRUCTION ELEMENT WITH THE FORMING OF ANY, FIRE-RESISTANT OR FLAME-RESISTANT MATERIAL AND AN INSULATING LAYER WITH A STRONGER THERMALLY INSULATING RESP. A DILUTION-COMPENSATING COAT. - Google Patents

Description

, * *

Br / Bl / lh / 76

Fire-resistant or flame-resistant composite construction element with a molding of any fire-resistant or flame-resistant material and an insulating layer with a stronger thermal insulating capacity or. a dilation-compensating layer.

The invention relates to a refractory or flame-resistant composite construction element with a molding of any refractory or flame-resistant material and an insulating layer with a stronger thermal insulating capacity, respectively. a moisture-compensating layer, as well as a method of manufacturing such composite construction elements.

Composite construction elements are already known which, in addition to forming a random refractory material, also have an insulating layer. The reason for this is that refractory molded articles with good mechanical properties generally have a high thermal conductivity, so that in certain applications where greater heat losses are to be avoided, it is advantageous to still provide such a shaped article of an insulating layer with a stronger thermal insulating capacity.

The object of the present invention is to provide improved refractory or flame-resistant composite construction elements of the above-mentioned type, wherein the insulating layer consists essentially of a ceramic fiber material and yet is very tightly bonded to the shaped product of any refractory material and simultaneously property of good wear resistance and relatively high strength.

The composite construction element according to the invention, as described further in the characterization of claim 1, serves to solve this problem.

Preferred embodiments are further described in claims 2-10.

8200597 * * -2-

The invention further relates to a method for the production of such composite construction elements according to the invention, which methods are further described in claims 11-16 *. For the manufacture of the composite construction elements according to the invention used ceramic fibers or mineral fibers can be any conventional fiber of this type, for example rock wool or aluminum silicate fibers with particularly high A 2 O 10 contents within the range of 45-95% by weight. Of course, mixtures of different ceramic fibers can also be used.

The clay 15 used for the production of the composite construction elements according to the invention can advantageously be a conventional clay or a special binder clay, bentonite. This clay is usually used in an amount of 2-15 parts by weight per 100 parts by weight of the ceramic fibers.

Furthermore, up to 10 parts by weight of other refractory additives can be used in the production of the composite construction elements according to the invention, the advantages of which are porcelain flour, chamotte onion or corundum spheres, also hollow.

Advantageously, the total amount of clay plus 25 other refractory additives is 20 parts by weight per 100 wt. parts of the ceramic fibers.

The other extra fine constituents optionally used in the manufacture of the composite construction elements according to the invention, such as extra fine 30-12 ° 3 and / or extra fine SiCl and / or aluminum hydroxides and / or extra fine magnesium oxide and / or extra titanium dioxide and / or extra fine chromium oxide are components known in the art in the field of refractories. The term "extra fine *" with regard to the above-mentioned components is hereby used to mean that these components are present in extremely finely ground or even in a colloidal state. In particular when using such materials in a colloidal state, 8200507 * * * Such as colloidal SiO2 or colloidal aluminum oxide, it is possible to use only small amounts of binder, namely in the vicinity of the lower limit of one part by weight of such a binder.

The phosphate binder used in the manufacture of the composite construction elements according to the invention is a conventional phosphate binder, the proportions by weight of which refer to the p2 ° 5 in the binder concerned.

Examples of such phosphate binders are sodium polyphosphate with a polymerization degree of n-4 and preferably with a polymerization degree of 6-10. A further phosphate binder is monoaluminum phosphate, which is a commercially available product both in solid, ground form and also as an aqueous solution with 50% by weight MAP.

In addition, customary plasticizers can be used in the manufacture of the composite construction elements according to the invention, which are, for example, surfactants or in particular methyl cellulose.

In addition, organic binders can be used in the production of the composite construction elements according to the invention, examples of which are molasses, sulphite phthalogue and in particular methyl cellulose.

In a preferred embodiment of the composite construction elements according to the invention, in the manufacture thereof the ceramic fibers are used as exposed fibers. For this purpose, commercially available fibers, in their delivered condition, are introduced into a turbo-mixer (manufactured by Drais-Turbulent-Schnellmischer), in which the fibers usually supplied as fiber bundles are converted into digestible fibers. Such a turbb mixer consists of a mixing unit with fast-rotating blade heads, whereby any agglomerates present in the commercially available fibers, which are partly present in highly compacted form, are made accessible without the fibers being crushed or crushed to an unacceptable degree. .

8200597 -4-

The composite construction elements according to the invention can be manufactured according to two different methods.

In the first method, a mixture of 100 parts by weight of ceramic fibers, 2-15% by weight, is first introduced in a step a). parts of clay and / or extra fine A 2 O 2 and / or extra fine SiO 2 and / or aluminum hydroxides and / or extra fine magnesium oxide and / or extra fine titanium dioxide and / or extra chromium oxide, if necessary not more than 10 parts by weight of other refractory additives 10 and 1-8 parts by weight of phosphate binder, calculated as Ρ,,, Ο., and optionally 2-100 parts by weight of added plasticizer are placed in a blender. A conventional Drais mixer or Eirich mixer can be used as the mixing device.

The finished mixture is then pressed on one side of a molding of any refractory material in step b), but this requires a compaction with a yolum factor of at least 3 and advantageously of 5-8.

This application by pressing can take place, for example, in the case of a molded stone, such that the mixture prepared in step a) is first brought into the mold and then the molding of arbitrary wall-solid material is placed thereon and then a compression is carried out. The reverse method is also possible, that is to say in the form that a molding of arbitrary refractory material can first be placed and a mixture as achieved in step a) is then applied to this molding of this refractory material, after which the pressing is carried out under the specified compaction.

Forming an insulating layer on the outside of a pipe is particularly simple. To this end, the already finished tubular blank is made of random, refractory; material is brought into a mold with a diameter greater than the external diameter of the refractory tube and the gap between the refractory tube and the core is filled as the mixture already prepared in step and either stamped or optionally pressed.

In another embodiment, after the preparation .8 2 0 0 5 9 7 fr * -5- ► of the mixture, a fiber granulate b ^), b ^) or b ^) or a mixture thereof, to be further described below, is briefly mixed mixing is incorporated into the mixture and this mass is then applied by compression on at least one side of the blank 5 of any refractory or flame-resistant material under compression. In the case of the use of an above-described mixture without the addition of a fiber granulate, the compaction during application by compression must take place with a volume factor of at least 3, 10 advantageously this compaction factor is between 5 and 8.

The maximum compaction factor that can be achieved in conventional pressing is of the order of about 12-14. If one of the above-mentioned fiber granulates is added to the mixture, such a strong compaction is not possible, but the compaction factor must be in each. approximately 1.5. A range of volume factors, which is advantageous when using a fiber granulate-containing mixture, is between 2.5 and 4. The reason for this smaller compaction factor lies in the fact that the fiber granules can no longer be compressed so strongly in this applies in particular to fiber granules b ^) and b ^) already compacted during their preparation -

Advantageously, the weight ratios of the mixture, without its water content, amount to fiber granulate (fiber granulate! From 20:80 to 80:20. The addition of a fiber granulate naturally requires more production water, so that the total amount of water added must be increased However, this can be easily determined by simply testing for 30 minutes.

In another embodiment of this method, one of the fiber granulates b ^) or b ^) to be described below, optionally with the addition of a further binder, in particular of an inorganic binder, and preferably of one of the above-mentioned phosphate binders. using agents with an appropriate amount of water, this amount of water when using dissolved binders may also be provided by the water in the 8200597-6 solution, the amount of water usually being 2-30 wt. parts per 100 parts by weight of fiber granulate. The amount of water depends on the fiber granulate used, in particular this applies when the fiber granulate is used, which is used both in dried and in tempered or roasted condition. However, it is possible to determine the amount of water required in each case by simple preliminary tests. Instead of one of the fiber granulates b) or b2) or a mixture thereof, a fiber granulate b. or b ^) are used together with another third fiber granulate b ^) to be described below, for the preparation of which only organic binder was used.

The advantage of the use of such a fiber granulate b ^} in a composite construction element according to the invention is that this fiber granulate b ^} in the composite construction element after its manufacture is at least partly still in the form of fibers. Since this fiber granulate contains only organic binder which, when the composite construction element is used, that is to say after initial heating, disappears therefrom by combustion at higher temperatures, individual granules of this fiber granulate remain in the composite construction element behind as discrete regions and retain the fibers contained within this fiber grain, with no or only slight bonding by inorganic birid agents. which have possibly penetrated, consequently 'a certain' elasticity by the ceramic fibers 30 which do not adhere closely to each other, so that the layer containing such fiber granulate is particularly suitable as a dilatation-compensating layer, because it has relatively good elastic properties possession. This also applies to some extent. when using the fiber granulate b2), whereby, due to the special preparation of the fiber granulate b2), only small amounts of phosphate binder penetrate into the fiber grain, so that even after a thermal treatment of a composite construction manufactured with such fiber granulate b2); 82 0 0 5 9 7 «'.

Element according to the invention, the interior of the fiber granulate remains elastic, so that the insulating layer resp. the dilation-compensating layer retains overall very good elastic properties. In another method according to the invention, first a matching to the molding of any refractory material, that is to say complementary layered molding of insulating material from one of the above-mentioned mixtures, is produced by pressing or stamping again under compaction with the stated volume factor. digd. This green bricks are then dried and / or tempered and / or baked and can then be glued or bonded to the green bricks of any refractory material. Conventional refractory sealant materials or also a concentrated solution of a phosphate binder can be used for pasting or sealing.

In this embodiment of the method according to the invention, in which a layer-shaped blank of insulating material is glued or glued to the blank of arbitrary refractory material, only drying of this layer-shaped blank of insulating material is advantageously carried out at step c), because in such a case, this layer-shaped formation of insulating material still has a certain elasticity, respectively. exhibits deformability, so that better adaptation to the molding of arbitrary fire material is possible.

The above explanations with regard to the advantages of the use of a fiber granulate-containing mixture in the manufacture of the insulating layer also apply in this case, that is to say, by the use of fiber granules and in particular of the fiber granules b2l and b ^} it becomes possible that the insulating layer resp. the dilation-compensating layer obtains particularly elastic and tension-absorbing properties.

As has already been explained above, the reason for this is probably that the ceramic fibers in the individual particles of the fiber granulate, in which no compaction was used in the preparation thereof, or in which a larger volume amount was used in the preparation thereof. 82 0 0 5 9 7 Organic binders and a smaller amount of phosphate binders were used, the elastic properties thereof being retained in the individual granules of the insulating layer when subjected to temperature, so that separate elastic or stress-absorbing areas or grains are present.

In the preparation of the fiber granules bb1 and b1), fibers which are advantageously used are also used, as described above, as in the preparation of the mixture.

The other starting materials used in the preparation of these fiber granules correspond to the starting materials, as already mentioned above.

The fiber granulates b), b2) and b11 are further described in patent applications ......... ........ resp.

........ in the name of the applicant, which were filed on the same date.

The preparation of this is explained in more detail below: 20)

This fiber granulate is prepared in such a way that already 100 parts by weight of ceramic fibers, 2-15 parts by weight of clay and / or extra fine A19Q and / or extra fine Si00 and / or aluminum.

25 's J A

hydroxides and / or extra fine magnesium oxide eri / or extra fine titanium dioxide and / or extra fine chromium oxide, optionally at most IQ parts by weight of other refractory additives and 1-8 parts by weight of phosphate binder, if necessary with a plasticizer in a mixing device. mixed with about 2-100 parts by weight of water, b) from the step a) the mixture is compacted with a volume factor of at least 3, and c} the product obtained in step b} is dried and / or at temperatures of 250-600 ° C thermal, treated 35 and / or burned at higher temperatures and then comminuted to the desired grain size.

The composition mentioned here corresponds to the composition as it is stated above with regard to: 8 2 0 0 5 9 7-9 in the insulating layer resp. dilation-compensating layer present mixture was described. In the preparation of the fiber granulate, the compaction in step b) is preferably carried out with a volume factor of. 5-8. The amount of water added in step a) 5 depends on in which device of the compaction the compaction is carried out with a volume factor of at least 3. When using a briquette machine or a turntable tube, an amount of water from 2 to 25 parts by weight is generally sufficient, while when using an extruder neck for compacting, up to even 1.00 wt. parts of water must be added, because this requires a more plastic mass.

Fiber granulate b2) 15

This fiber granulate b) is prepared in such a way that a) 100 parts by weight of ceramic fibers are mixed with 10-40 parts by weight of water in a mixer, b) to the mixture obtained in step a). 20 wt. parts of clay 20 and / or extra fine Al2O3 and / ° extra fine SiO2 and / or aluminum hydroxides and / or extra fine magnesium oxide and / or extra fine titanium dioxide and / or extra fine chromium oxide, as well as 0-10 parts by weight of solid organic binder. 25 ml on the result obtained in step b): mixture 0.5-4 parts by weight of an organic binder, calculated as a solid, in solution, as well as 1-8 parts by weight of phosphate binder, calculated as P 2 O, are applied and passed through.

mixing are recorded, and d) the mixture obtained at step cl is dried and granulated.

Have them 1 granul aatjg ^}

This fiber granulate b ^ 1 is prepared in such a way that a) 100 parts by weight of ceramic fibers, 2-15 parts by weight of clay and / or extra fine and / or extra fine SiC> 2 and / or aluminum. hydroxides and / or extra fine magnesium oxide and / or extra ....... fine titanium dioxide and / or extra fine chromium oxide, optionally 82 0 0 5 9; -10- at most 10 parts by weight of other refractory additives and 1-10 parts by weight organic binder, calculated in solid form, are thoroughly mixed in a mixer with about 5-100 parts by weight: water and 5 b) the mixture obtained in step a) is compacted with a volume factor of at least 3, dried and then comminuted to the desired grain size.

As in the preparation of the fiber granulate b) in this case, the amount of water to be added thereof is; Depending on which compaction device the compaction of the mixture obtained in step a) takes place, in conventional compaction devices, such as briquetting presses and rotary presses, 5-25 parts by weight of water are required, while in compaction in a strand press 15 to even 100 parts by weight of water can be added to prepare a more plastic starting material in step a).

As for details regarding the preparation of the fiber granulates b ^ 1, b ^) resp. (b)) reference is made to the above-mentioned patent applications in the name of the applicant. The preparation of these fiber granulates is illustrated in more detail by the following examples.

In these examples, two different types of ceramic fibers were used, namely

Al ceramic fibers of the system Al20 ^ -Si02 by 47%

Al2 O3 and 53% SiO2, the maximum operating temperature of which is at 1260 ° C, and

B1 ceramic fibers of the system A1 ^ 0 - Si0- with 95% 30 Δ * c A12C> 3 and 5% Si02, which allow higher operating temperatures above 1500 ° C.

In the following examples, the amounts quoted are in parts by weight unless otherwise stated.

Example I 35

In an Eirich mixer, 100 parts by weight of the ceramic fibers A), 10 parts by weight of binder clay with an Al 2 O 3 content of 35% by weight and 1.5 parts by weight of dry methyl cellulose were powdered and therein for 10 min.

82 0 0 5 9 7 -II- mixed together. Then, 10 parts by weight of a 50% by weight monoaluminum phosphate solution and 2 parts by weight of water were sprayed onto the mass in the mixer with continuous further mixing and mixed for an additional 30 minutes.

The product removed from the mixer was pressed in a multi-stage press at a press pressure of 30 N / mm into a plate-shaped product with a thickness of 30 mm, whereby a compaction with a factor of 5.5 was achieved.

The resulting plate-shaped product was then dried in an oven at 110 ° C for 24 hours and then burned at different temperatures for 24 hours each time and then comminuted to a maximum grain size of 3 mm.

The granulate had the following properties:

15 TABLE A

Burning temperature (° C). 800 1350 1510

Apparent density of the grains R (g / cm3) 1.34 1.52 1.77

Specific weight S (g / cm) 2.60 2.70 2.75

Pore volume, Pg (% by volume) 47.7 43.7 35.6

Chemical analysis (%) A ^ O ^ 44.7

SiO2 50.7 P205 2.95 25

Example II

The procedure of Example 1 was repeated, using a turbo-mixer, however, which digested the fibers. The pressing pressure at step b) was 10 resp.

15 N / mm, the compaction was at a factor of 4 resp. 5.

After burning for 24 hours at 1350 ° C and comminuting, a granulate with the following properties was obtained:

TABLE B

Compression pressure (N / mm2) 10 15 R (g / cm3) 0.7 1.02 3

Density (g / cm) 2.7 2.7

Pg (vol.% 1 74 63 '82 0 0 5 9 7 '-12-

Example III

The procedure of Example I was repeated, however increasing the amount of monoaluminum phosphate solution to 15 parts by weight and the amount of water to -5 parts by weight at a shortened mixing period of 20 minutes. After burning for 24 hours at 1350 ° C and comminuting to the desired grain size, the granulate had the following properties:

. TABLE C

10 R (g / cm3) 1.29 S (g / cm3) 2.69

Pg (vol.%) 53.8

Example IV

The procedure of Example 1 was repeated, but with 8 parts by weight of chamotte flour added in step a). Furthermore, only 8.3 parts by weight of 50% by weight of monoaluminum phosphate solution but only 4 parts by weight of water were added to this mixing step.

The compression pressure at the compaction step b) was 2 30 N / mm, which yielded a compaction with a volume factor of 5.2.

The resulting plate-shaped product was dried at 180 ° C, after which samples were burned at the different temperatures listed in Table D below.

Then the dried resp. crushed roasted product to a maximum grain size of 3 mm.

The obtained granulate had the following properties; shelves.

30 TABLE D

Treatment temp. (° C) 180 800 1200 1300 1500

Apparent density of grains R (g / cm) 1.30 1.26 1.31 1.34 1.48 3

Density (g / cm) 2.60 2.60 2.65 2.68 2.72 35 Pg (vol.%) 50.0 51.5 50.5 50.0 45.6

Example V

The procedure of Example X was repeated, using, however, 10 parts by weight of extra fine colloidal aluminum hydroxide instead of the binder clay.

This aluminum hydroxide was in the form of a very viscous solution. At the mixing stage, 8 parts by weight of 50% by weight monoaluminium phosphate solution and 3 parts by weight of water were added.

The compaction at the pressing stage was carried out at a 2 press pressure of 30 N / mm, yielding a volume factor of 5.4 at this compacting stage.

The further treatment was carried out as described in Example 1, the drying temperature however being 120 ° C and the samples of the plate material at the; Different temperatures listed in Table E below were fired. The material was then granulated as in Example I.

: 15 The fiber granulate had the following properties:

TABLE · · E

Treatment temp. (° C) 120 800 1200 1300 1500

Apparent density of grains, R (g / ciiT) 1.34 1.32 1.38 1.39 1.} 44 20 Density (g / cm ^) 2.72 2.72 2.77 2.79 2.83

Pg (vol. S) 50.7 51.5 50.2 50.1 49.1

Example VI

The procedure of Example 1 was repeated except that, instead of the 50 wt.% Fs monoaluminum phosphate solution, 4.5 parts by weight of solid sodium polyphosphate were used in the mixing step. amount of water was 9 parts by weight.

; At the compaction under a pressure of 30 N / mm 30, a compaction with a volume factor of 5.3 was achieved.

The further treatment was carried out as described above, drying at 120 ° C. In the table below, the properties of the fiber granulate obtained according to the procedure of Example I from the dried product or the product are shown in the table below. from the products obtained at the different burning temperatures.

82 0 0 5 9 7 »t f -14-

TABLE F

Treatment temp. (° C) 120 800 1200 1300 1500

Apparent density of grains, R (g / cm3) 1.22 1.1? 1.32 1.38 1.41

Density (g / cnr) 2.60 2.61 1.65 2.69 2.73 5 Pg (vol.%) 53.1 54.4 50.1 48.6 48.4

Example VII

In this example, compaction was performed by compression molding.

First, 100 parts by weight of ceramic fibers B) were mixed in an Eirich mixer for 10-20 minutes with 1.5 parts by weight of dry methyl cellulose. Then in the. in operation mixer 10 parts by weight of the binder clay used in Example 1 and 2 parts by weight of extra fine chromium oxide with a maximum particle size of 63 µm were added, after which it was mixed for a short time and then 10 parts by weight of 5% by weight. % strength monoaluminum phosphate solution and 80 parts by weight of water were added, followed by thorough mixing. The extruding was done in a conventional extruder, the nozzle having a diameter of 250 x 190 mm. The volume factor achieved in the yerd compacting was 3.9. The material exiting from the nozzle was cut to suitable clod lengths, which were first dried at 110 ° C for 24 hours and burned at the different fire temperatures shown in Table G for 24 hours each. Thereafter, the treated clods used as samples were broken into a grain granulate with a maximum grain size of 6 mm.

The properties determined on this fiber granulate were as follows.

TABLE G

Treatment temp. (° C). 110 900 1100 1300 1500

Apparent density of grains, R (g / cm3) 0.90 0.87 0.92 1.00 1.27 3

Density (g / cm) 2.60 2.61 2; 63 2.65 2.73

Pg (vol.%) 65.4 6.66 65.0 62.2 53.5 ~ Y * "...... .......

82 0 0 5 9 7 i ~ φ Μ

Example VIII

First, 100 parts by weight of fibers with 1.5 parts by weight of dry methyl cellulose were digested in a turbo-mixer for 20 minutes, after which 10 parts by weight of solid SiO 2 in solid form were added and mixed with the fibers. Then, 8 parts by weight of solid, powdered monoaluminum phosphate was added to 8 parts by weight of water and mixing was continued for 12 minutes.

The resulting crumbly mixture was compacted in a briquette machine at a volume factor of 4.9, then dried at 120 ° C for 24 hours, and another sample was heat-treated without prior drying for 24 hours at 400 ° C and a further sample also burned at 1000 ° C for 24 hours without prior drying.

The resulting treated samples were comminuted to a maximum grain size of 4 mm and the following properties were measured on the obtained granulates:

20 TABLE H

Treatment temp. <° C) 120 400 1000

Apparent density Granules, R (g / cm3) 1.15 1.10 1.13 3

Density (g / cm) 2.58 2.57 2.65 25 Pg (vol.%) 55.4 57.2 57.3

Preparation of fiber granulate. b2)

In this preparation, the above-mentioned ceramic fibers A resp.

30 B used.

Examples 1X-X1

The following recipes were used, the amounts stated being expressed in weight amounts.

- 82 0 0 5 9 7 -16-

Example_ -_IX ___ X_XI

Fibers A 100 JL00 100 H20 30 15 40

Bentonite 10 - 15 5 A120 5 5

TiO2 - 21

Methyl cellulose, solid. 4 - 3.5

Sulphite phalOG, solid - 5 -

Sulphiteaphthalic solution,:.

10% by weight - 2 -

Methyl cellulose solution, 5 wt% 0.5-3

Monoaluminum phosphate, solid 4 - 8;

Sodium polyphosphate, solid - 2.5 ^ The ceramic fibers were first introduced into an Eirich mixer, after which the stated amounts of water were sprayed on and mixed for 10 min.

Subsequently, the bentoniest, the Al2 O2 and resp. Ti0o, and the solid methyl cellulose resrp. the solid 20-2 sulfite phalog was applied and mixing was continued for an additional 8 minutes. Thereafter, solutions of sulfitaphthalog resp. methyl cellulose, to which the finely divided solid phosphate binders have been added, was sprayed and mixed for an additional 10 minutes.

25

The yeast crumbly mixture was taken out of the mixer.

The crumbly mixture of Examples IX-XI was dried at 120 ° C for 6 hours and then on a crushing roller? comminuted to a maximum grain size of 4 mm.

3Q

The properties measured on the products were as follows:

Example _ '' '' _ IX_ 'X XI

Apparent density (g / cm3) 0.22 0.14 0.40

35 Examples XII-XIV

The procedure of Examples IX-XI was repeated, but in this case, exposed ceramic fibers B were used. The fibers were digested

Tl 8 2 0 0 5 9 7 * * -17- in a turbo mixer (Drais), for which the fibers were treated for 5 minutes in this fast-rotating mixer equipped with knife heads. These digested fibers B were then transferred to an Eirich mixer, in which the further components according to the recipes of Examples IX-XI were added.

A fiber granulate was also prepared from the products of Examples XII-XIV:

The properties determined on the products were as follows:

Example XII XIIII XIV

3

Apparent density (g / cm) 0.25 0.17 0.45

Preparation of fiber granulate b ^) ^ As in the preparation of the fiber granulate b ^), ceramic fibers A resp. B used with the above compositions.

Examples XV-XIX

The following recipes were used:

Example XV XVI XVII XVIJX ~ XIX

Ceramic fibers A 100 - - 50

Ceramic fibers B - 100 100 100 50

Binder clay (with 35% Al2 O3) 15 6 4 - 25 Chromium oxide, <63 pm - 4 4 - -

Colloidal SiO2 - - 624

Colloidal A12C> 3 "- · - 6

Methyl cellulose, solid 6 - 4 1

Sulphite phalog, solid - 7 2 -. - 30 Chamotte flour 2 - - - - - IJater 25 IQ 15 12 25

In an Eirich mixer, the ceramic fibers with binder clay resp. the other ingredients are mixed for 5 minutes, after which the organic binder resp. binder mixture and finally the water was added. A total of 20 minutes was mixed.

This mixture was compacted in the briquetting machine (manufac- turing 8200597-18KKHD) with the stated volume of factors, then dried at 120 ° C for 12 hours and then comminuted to a maximum grain size of about 6 mm. The following properties were determined on the fiber granules obtained:

Example XV XVI XVII XVIII XIX

Apparent density, * R (g / om3) 1.25 1.09 1.15 1.20 1.23

Compaction factor 5.4 '7.2 6.8 6.0 6.5

Pore volume, Pg, (vol.%) 49.5 69.7 68.0 53.8 62.6

Examples XX-XXIV

The procedures of Examples XV-XIX were repeated, however, using decomposed fibers were used. The fibers were digested in the course of 5 minutes in a turbo mixer (Drais). Then the other additives were added and. was mixed for 2 more minutes.

2q. The compaction took place on a hydraulic press to form stones of 250 x 125 x 30 mm, which were dried at 120 ° C for 12 hours and then crushed to a maximum grain size of 6 mm. The following properties were measured on the fiber granules obtained:

Example XX XXI 1CXII ΧΧΠΙ XXIV

R (g / cm3) 17100 0.95 1.01 1.04 1.09

Compaction factor 6.0 7.9 7.2 6.9 7.3

Pg (vol.SI 56.0 75.3 Vil, 7 59.9 66.6 30

Example XXV

The recipe of Example XX was used, however, 80 parts by weight of water were included in the mixture. The compaction took place in an extruder, the cross section of the nozzle in this case being 250 s 190 mm. The raw clods removed from the strand press were cut to suitable lengths and dried at 120 ° C for 24 hours. The dried clods obtained were then broken to a maximum grain size of 3 mm. The following properties were measured on the fiber granulate obtained - 8200597 -19: R (g / cm ^) 0.95

Compaction factor 3.2 5 Pg (vol.%) 62.7

The manufacture of the composite construction elements according to the invention is explained in more detail below with reference to the following examples.

10 Example XXVI

A fiber mass was prepared using the following ingredients:

Parts by weight

Ceramic fibers A 10015 Binder clay with 35% A ^ O ^ 10

Chamotte flour, <63 μιη 10

Mono aluminum phosphate, solid 6

The above components were placed in a forced circulation mixer (type Zyklus), mixed for 2 minutes, then 25 parts by weight of water were added and mixed for another 15 minutes.

In a top-open sheet metal molding box, a baked pipe of pipe earth was arranged perpendicularly, so that a gap remained between the outside of this pipe and the interior of the tin forming box. This gap was filled with the previously prepared fiber granulate and tamped using a compressed air hammer. The rough top was then leveled to allow binding to occur. The composite construction element thus obtained was dried at 120 ° C for 24 hours and then baked at 135 ° C for 5 hours.

During baking, the fiber mass, i.e. the insulating layer, shrank on the tube and formed. an insoluble assembly with the refractory inner tube.

Such a composite construction element as well as a gas discharge pipe are used, namely for gases, which have to be transported at high temperatures of for instance 1100 to 82 0 0 5 9 7 -20 - 1150 ° C and / or high gas velocities. an insulating material without an inner tube of refractory material, in such a case a tube of silicon carbide, cannot be used.

Example XXVII

A fiber material with the following composition was used:

Parts by weight 10 Ceramic fibers B 100

Clay (about 40 wt.% A ^ O ^) 4-, a ^ 2 ° 3 ^ an 0/064 mm 6

Monoaluminum phosphate, solid 6 The ceramic fibers B were first washed for 4 min.

unlocked in a turbo mixer. The further processing of the mass took place according to example XXVI.

As the inner tube, a 25 cm diameter silicon carbide tube was used. After tamping the green green bricks, it was dried at 300 ° C for 24 hours, then heated to 1000 ° C using an electrical heating element placed in the inner tube. A large number of temperature cycles were carried out, that is, the composite construction element was each allowed to cool to ambient temperature and then heated again to 1000 ° C. The composite construction element had an excellent service life, while the insulating layer adhering thereto showed no cracks or scattering phenomena. This means that the insulation layer .30. despite the greater strength, the forming fiber mass is sufficient. elastic to compensate for the different thermal expansions of the silicon carbide of the inner tube on the one hand and of the fiber mass forming the insulating layer on the other.

Examples XXVIII-XXXIII

The procedure used in Example XXVI was repeated, adding to 120 parts by weight of the mixture concerned the following 82 0 0 5 9 7 -21-pebble granulates in the amounts indicated, as well as further amounts of water, listed in Table I below, and added for 2 was mixed in the mixer for minutes. However, in Example XXIX, XXXI, XXXIII, in contrast to the amount used in Example XXVI, 7.5 parts by weight of mono-aluminum phosphate were used. With this mass, composite construction elements with excellent properties could be produced according to the procedure of Example XXVI.

TABLE i '

10 Example_ XXVIII XXIX XXX XXXI ΧΧΧΙΙ XXXIII

Fiber granulate, type b ^) b ^) b ^) b2) b ^) b ^)

- Fiber granulate from example. IV XI XII XVIII XIX

Quantity (parts by weight) 50 200 40 300 20 400

Example XXXIV

The mixture described in Example XXVII was prepared, but it was not pressed on a plate press with a compaction: ·· a volume factor of 5.2 to plates with a thickness of 3 mm. The plates were dried at 120 ° C for 5 hours. Pieces were cut from these slabs with the aid of a brick (405 x 135 mm), on which one side was cemented with chamotte stones with a refractory sealant. ' The composite construction elements obtained in this way had a dilation-compensating layer.

25 Examples XXXV-XL

The amounts (in parts by weight) of fiber granulate (granules of the types mentioned), which were prepared in the examples also listed in Table J, listed in Table J below were placed in an Eirich mixer, to which 30 parts per 100 parts by weight of the fiber granulate or the fiber granulate mixture 5 parts by weight of a 50% by weight monoaluminum phosphate solution and 10 parts by weight of water were applied, followed by mixing for a further 3 minutes The masses obtained were also placed around an inner tube of refractory refractory, whereby composite construction elements with excellent properties were obtained.

82 0 0 5 9 7 $ -22-

TABLE J

Example_XXXV XXXVI XXXVII XXXVIII ΧΙΙΓ XL

Fiber grain. " type b ^) 100 - 50 25 25 v. ex. IV III VI VII '5 Fiber grain. type b2) - 100 50 50 25 "

v. ex. XII XII XIII XIV

Fiber grain. type b ^) - ~ ”25 50

v. ex. XVII XVIII

In the composition of the mixtures of fiber granules, a granular fraction with a maximum particle size of 3 mm and a content of less than 1 mm of about 30% by weight was used.

8200597

Claims (16)

1. Fireproof or flame-resistant composite construction element with a molding of any fire-resistant or flame-resistant material and an insulating layer with a higher thermal insulating capacity. a dilatation-compensating layer, characterized in that the insulating layer resp. the dilation-compensating layer is bonded tightly to the blank and is formed from a) 100 parts by weight of ceramic fiber, 2-15: parts by weight of clay and / or extra fine and / or extra fine SiO2 and / or aluminum hydroxides and / or extra fine magnesium oxide and / or extra fine titanium dioxide and / or extra fine chromium oxide, optionally at most 10 parts by weight of other refractory additives • and 1-8 parts by weight of phosphate binder, calculated as ... P20g, and optionally, an added plasticizing agent or 15 b) optionally with further addition of a binder of one of the following fiber granulates or a mixture of such fiber granules (b) of a first fiber granulate prepared by mixing 100 parts by weight of ceramic fibers, 2-15 parts by weight of clay 20 and / or extra fine and / or extra fine SiO2 and / or aluminum hydroxides and / or extra magnesium oxide and / or extra fine titanium dioxide, and / or extra fine chromium oxide, optionally at most 10 parts by weight of other refractory additives, 1-8 wt. parts of phosphate binder, 25 calculated as P2Os, optionally with addition of plasticizer with 2-100 parts by weight of water, compacting this obtained mixture with a volume factor of at least 3, drying and / or heat treatment at 250 ° C to 600 ° C and / or firing at higher temperatures of the obtained product and then by crushing it to the desired grain size, b2) of a second fiber granulate prepared by mixing 100 parts by weight of ceramic fibers with 10-40 parts by weight of water, adding and mixing 5-20 parts by weight of clay and / or extra fine A12Q3 and / or extra fine SiO2 and / or aluminum hydroxides and / or extra fine magnesium- 82 0 0 5 9 7 ...... -24-oxide and / or extra fine titanium dioxide and / or extra chromium oxide, as well as 0-10 parts by weight solid organic binder, adding and mixing 0.5-4 parts by weight organic binder in solution as well as 1-8 parts by weight. 5 parts of a phosphate binder ,. calculated as P 2 O, drying the product obtained and comminuting to the desired grain size, or a mixture of one of the grain granules (b) and / or b2) with a third fiber granulate (bl) prepared by mixing 100 parts by weight of ceramic fibers with 2-15 wt. parts of clay and / or extra-fine Al2 O3 and / or extra-fine SiO2 and / or aluminum hydroxides and / or extra-fine titanium dioxide and / or extra-fine chromium oxide, possibly with a maximum of 10 parts by weight. 5. further refractory additives, 1-10 parts by weight of organic binder, calculated in solid form, and 5-100 parts by weight. parts of water, compacting the obtained mixture with a volume factor of at least 3, drying the product and calculated to the desired grain size, 20 or cl of a mixture of a) and one or more of the fiber granules b ^), b2) and b ^}. 2. Composite construction element according to claim 1, characterized in that it contains bentonite as a clay component in the insulating layer. Composite construction element according to claim 1, characterized in that it contains porcelain flour, chamotte or corundum hollow spheres in the insulating layer as a further stable additive. Composite constructional element according to claim 1, characterized in that the insulating layer contains sodium polyphosphate as the phosphate binder. 5. Composite construction element according to claim 1, characterized in that the insulating layer contains phosphorus binder monoaluminum phosphate. Composite construction element according to claim 1, characterized in that it contains methyl cellulose in the insulating layer as a plasticizer or organic binder. 82 0 0 5 δ 7 ....... -25- Composite product according to claim 1, characterized in that it contains molasses or sulphite phalogue as organic binder. Composite product according to one or more of the preceding claims, characterized in that it contains ceramic fibers which are released as ceramic fibers. Composite product according to one or more of the preceding claims, characterized in that it is a tubular body with an external insulating layer. Composite product according to one or more of the preceding claims, characterized in that in the insulating layer there are hollow spaces, in particular guideways, or hollow spaces for accommodating pipes or yer reinforcements. 11. A method for manufacturing a construction element according to claim 1, characterized in that a) 100 parts by weight of ceramic fibers, 2-15 parts by weight of clay and / or extra fine and / or extra fine SiO and / or aluminum hydroxides and / or extra fine magnesium oxide and / or extra 20 fine titanium dioxide and / or at most 10 parts by weight of other refractory components, 1-8 parts by weight of phosphate binder, calculated as P2®5 ', optionally with the addition of a plasticizer in a mixer thoroughly with 2-25 wt. parts of water are mixed, the mixture obtained in step a) is pressed at least on one side of a blank of any refractory or flame-resistant material with a compaction with a volume factor of at least 3, cl the amount in step b). The obtained green product of the composite construction element is dried and / or tempered at temperatures of 250-600 ° C and / or burned at temperatures of 600-160 ° C. 12. Process according to claim 11, characterized in that, at step al ha ', the preparation of the mixture comprises a further fiber granulate with the composition indicated in claim 1 b, l, b2) or b, l or a mixture thereof is taken up for a short time by mixing, the densification then taking place in step b) with a volume factor of at least 1.5%, 82.0 0 5 9 7 * V -26-. 13. A method of manufacturing a composite construction element according to claim 1, characterized in that a fiber granulate with the composition or b2) or a mixture thereof or a mixture of the fiber granulate b specified in claim 1 b ^) with a fiber granulate b ^) or b ^) or a mixture thereof with water, optionally with further addition of phosphate binder or organic binder, with water for a mass which can be processed by pressing XO, such that this mass is applied on at least one side of a molded article: pressed from any refractory or flame-resistant material and the resulting green article is dried and / or tempered at temperatures of 250-600 ° C and / or baked at X5 temperatures of 600-1600 ° C * Method for manufacturing a composite construction element according to claim 1, characterized in that already 100 parts by weight of ceramic fibers, 2-15 parts by weight of clay and / or 20 or extra fine Al2C> 3 and / or extra fine SiO2 and / or aluminum hydroxides and / or extra fine magnesium oxide and / or extra fine titanium dioxide and / or extra fine chromium oxide, optionally at most 10 parts by weight of other refractory additives, 1-8 parts by weight of phosphate binder, optionally with the addition of a plasticizer, is thoroughly mixed in a measuring device with 2 to 25 parts by weight of water, and optionally another fiber granulate with the composition b), b) or b), or a mixture thereof, as stated in claim 1, by mixing for a short time is recording. B) the mixture obtained in step a) into a molded product with respect to any refractory or flame-resistant material, complementary insulating layer or. dilation-compensating layer member is formed by compaction with a volume factor of at least 3 when using the mixture without fiber granulate (granules). or of at least 1.5 when using a fiber granulate or fiber granules for molding, c) the green green layer of insulating layer or layer obtained in step b). dilatation-absorbing layer on the green brick is dried and / or tempered at temperatures of 250-600 ° C and / or baked at temperatures of 600-1600 ° C, 82 0 0 5 9 7 -27- and d) the molded article obtained in step c) with the insulating layer resp. expansion-compensating layer with the shaped product of the respective refractory or flame-resistant material connected by surfaces or sealants. 15. A process for the production of a composite product according to claims 11-14, characterized in that fibers which are disclosed are used as ceramic fibers in the preparation of the mixture or of the fiber granulate. Method of manufacturing a composite construction element according to any one of claims 12, 15, 14 or 15, characterized in that per 100 parts by weight of the mixture, at most 400 parts by weight of one of the fiber granules b ^), or one of these may be added. 82 0 0 5 9 7