DE102010010957A1 - Building material with heat-insulating property - Google Patents

Abstract

The invention relates to building material with heat-insulating properties, the building material containing particles (1) of petroleum coke, in particular calcined petroleum coke, and the building material being a non-metallic-inorganic material and / or a natural substance and / or a plastic other than Polystyrene.

Description

The invention relates to a building material with heat-insulating property.

Technological background

There are many building materials with heat-insulating properties. In order to obtain sufficient thermal insulation properties in the construction sector, more and more efforts are made. Usually, additives are added to conventional building materials which lower the thermal conductivity and thereby improve the thermal insulation of the building material. In addition, there are other requirements for building materials, such as increased reflection of infrared radiation (heat radiation and / or cold radiation) and protection against electrosmog.

State of the art

From the WO 2008/089085 A1 For example, a construction material in the form of a fiberglass material is known in which the fibers are provided with a graphite coating in order to avoid electrostatic charging of the fibers. The coated fibers are used for insulation purposes in a wide variety of applications.

From the EP 1 749 805 is known a gypsum building material with increased thermal conductivity and a shielding effect against electromagnetic radiation. The gypsum building material is added to a regrind of compacted graphite expandate.

From the WO 2005/120146 is a brick with cavities whose cavities are coated with a material which reflects from an electrically conductive and / or infrared radiation, the material being graphite or mica.

From the DE 20 2008 014 415 U1 as well as from the EP 2 028 329 A1 is in each case a thermal insulation brick with cavities known, the cavities are filled with a thermal insulation material.

From the DE 197 28 543 A1 is known a polymer foam, which is added as an additive to reduce the thermal conductivity graphite.

From the WO 97/45477 Expandable styrene polymers are known which, based on the weight of the polymers, 0.05 to 25 wt .-% of soot particles in homogeneous distribution and can be processed to self-extinguishing foams having a density of ≤ 35 g / l.

From the EP 0 372 343 A1 For example, a polystyrene foam is known which contains soot particles with a particle size of 10 to 100 nm and a specific surface area of 10 to 1500 m ² / g.

From the WO 2008/141767 A2 It is known to add particles of graphitic material, for example graphitized coke, with a degree of graphitization of at least 0.2, preferably a graphitization degree of 0.3 to 0.95, to a composite material based on vinylaromatic polymers in order to increase their thermal insulation properties.

Synthetic graphite is produced by a thermal treatment at temperatures of about 2,800 ° C. The production of synthetic graphite is therefore particularly energy-intensive. In addition, there is also natural graphite, which mined and processed by mining. Both synthetic and natural graphite are capable of reflecting IR radiation. However, graphite has a comparatively higher thermal conductivity, which adversely affects the insulating effect of the building material when touching the graphite particles within the matrix (percolation).

task

The object of the present invention is to provide a novel building material with improved properties.

The above object is achieved in that the building material contains particles of petroleum coke, in particular calcined petroleum coke, and it is the building material is a non-metallic-inorganic material and / or a natural material and / or a plastic other than polystyrene.

• (a) kalzinierter Petrolkoks hat im Vergleich zu synthetischem Graphit eine deutlich günstigere Energiebilanz, da zur Kalzinierung des Petrolkoks lediglich eine weitaus niedrigere Temperatur von ca. 1200°C notwendig ist;
• (b) kalzinierter Petrolkoks besitzt im Vergleich zu synthetischem oder natürlichem Graphit eine deutlich geringere thermische Leitfähigkeit, was dazu führt, dass bei Erreichen der Perkolationsschwelle sich im Vergleich zu synthetischem bzw. natürlichem Graphit eine deutlich geringere Erhöhung der Wärmeleitfähigkeit einstellt, so dass die Wärmedämmung des Bauteils nur unwesentlich beeinflusst wird. In der Praxis kommt es häufig zu unvermeidbaren inselartigen Partikelanhäufungen innerhalb des Bauteils (so genannte „Perkolationsinseln”). Für diesen Fall ist die Verwendung von kalziniertem Petrolkoks im Vergleich zu Graphit besonders vorteilhaft, da es hierbei aufgrund der schlechteren Wärmeleitfähigkeit von kalziniertem Petrolkoks im Vergleich zu Graphit zu keiner nennenswerten Erhöhung der gesamten Wärmeleitfähigkeit des Bauteils kommt;
• (c) kalzinierter Petrolkoks ist im Gegensatz zu Graphit spröde und aus diesem Grund leicht zu mahlen, d. h. in die erforderliche Partikelform zu bringen;
• (d) kalzinierter Petrolkoks kann durch Einsatz geeigneter Mahltechnik in Partikel mit plättchenförmiger Form überführt werden;
• (e) im Gegensatz zu Ruß, der eine sehr hohe spezifische Oberfläche besitzt, ergibt die Verwendung von kalziniertem Petrolkoks-Partikeln den Vorteil, dass für den erforderlichen Wärmedämmeffekt Partikel mit im Vergleich zu Ruß sehr viel geringerer spezifischer Oberfläche zur Verfügung stehen; dies hat den Vorteil, dass, anders als z. B. bei Ruß, Flammschutzmittel, die für bestimmte Baumaterialien zwingend vorgesehen sein müssen, nicht über die Oberfläche absorbiert werden können. Aus diesem Grund ist es möglich, eine vergleichsweise geringe Menge an Flammschutzmittel einzusetzen. Flammschutzmittel sind extrem teuer;
• (f) Petrolkoks, insbesondere kalzinierter Petrolkoks, bewirkt darüber hinaus eine Abschirmung gegenüber elektromagnetischen Wellen, Elektrosmog und Ähnlichem.

The use of petroleum coke, in particular calcined petroleum coke, has the following advantages:

• (a) calcined petroleum coke has a much more favorable energy balance compared to synthetic graphite, as only a much lower temperature of about 1200 ° C is necessary for the calcination of petroleum coke;
• (b) calcined petroleum coke has a significantly lower thermal conductivity compared to synthetic or natural graphite, which means that, when the percolation threshold is reached, a significantly lower increase in thermal conductivity occurs compared with synthetic or natural graphite, so that the thermal insulation of the Component is influenced only insignificantly. In practice, unavoidable island-like particle accumulations within the component often occur (so-called " Perkolationsinseln "). For this case, the use of calcined petroleum coke compared to graphite is particularly advantageous because it comes here due to the poorer thermal conductivity of calcined petroleum coke compared to graphite to no significant increase in the total thermal conductivity of the component;
• (c) calcined petroleum coke is, in contrast to graphite, brittle and therefore easy to grind, ie to bring into the required particle shape;
• (d) calcined petroleum coke can be converted to particles of platelet form by use of suitable milling techniques;
• (e) in contrast to carbon black, which has a very high specific surface area, the use of calcined petroleum coke particles has the advantage that, for the required thermal insulation effect, particles with a much smaller specific surface area compared to carbon black are available; This has the advantage that, unlike z. As in soot, flame retardants, which must be provided for certain building materials imperative, can not be absorbed through the surface. For this reason, it is possible to use a comparatively small amount of flame retardant. Flame retardants are extremely expensive;
• (f) Petroleum coke, especially calcined petroleum coke, also provides shielding against electromagnetic waves, electrosmog, and the like.

The petroleum coke is expediently calcined petroleum coke, which is thermally treated at a temperature of about 1200 ° C. In this case, the volatiles present in the so-called green coke escape. For calcined petroleum coke there is no graphitization (0% degree of graphitization).

Particularly suitable are isotropic petroleum coke particles.

A particularly good efficiency arises when the petroleum coke particles have a platelet-shaped grain shape. They then act in the matrix of the building material like a multitude of tiny, disorderly arranged mirrors, which bring about optimal reflection of infrared radiation (thermal radiation or even cold radiation).

Advantageously, the petroleum coke particles have a particularly high aspect ratio, which is in particular in the range of 1-500, preferably 5-50, wherein the aspect ratio represents the ratio of the average diameter to the average thickness of the particles.

Advantageously, the petroleum coke particles may have an average particle size of from 1 .mu.m to 50 .mu.m, preferably from 1 .mu.m to 10 .mu.m.

Conveniently, the petroleum coke is added in such an amount based on the total weight of the building material that the thermal conductivity of the building material depending on the building material in question compared to a corresponding building material without petroleum coke by at least 2.5%, preferably at least 10%, more preferably at least 20% is reduced.

It is particularly advantageous if the petroleum coke is contained in an amount of 0.05 wt .-% to 10 wt .-% based on the total weight of the building material.

Is it a building material with a binder such. B. mineral fibers z. B. are fixed by means of resin to a fiber composite, or insulating materials made of natural fibers, in which the natural fibers are bound with a suitable binder, the petroleum coke particles are added to the binder so that they are uniformly distributed there.

Alternatively or additionally, the respective fibers or fiber mats may each be provided individually or in combination with a petroleum coke particle-containing coating. This can be done either by impregnation, dipping, spraying or similar technology. Conveniently, the petroleum coke particles are dispersed in a binder or a binder solution. Particularly advantageous for this purpose is a thermally or hydraulically curing binder.

According to another embodiment of the present invention, a petroleum coke particle-containing coating is used in a building material in the form of a fired shaped body. Preferably, the coating is in the region of the walls of the mold cavities of the shaped body.

Conveniently, the mold cavities of the molding can be completely filled with petrolkoksbeschichteten fibers or packing.

Alternatively, the building material is a hydraulically bonded molding, for. B. a concrete block or a plaster-containing molded body. In both cases, the addition of petroleum coke particles causes a significant improvement in thermal insulation.

Alternatively, the building material is a pasty, viscous mass that suitable to be applied by the user by brushing or filling.

Alternatively, the building material is foamed polymer material, which is preferably used as mounting foam and / or insulating foam. Again, the use of petroleum coke particles contributes to a significant improvement in the insulation effect. For example, in a two component system, the petroleum coke particles may preferably be added to one of the starting components or, e.g. B. in moisture-reactive polyurethanes, are added directly to the reaction component. When applied from the aerosol can, the petroleum coke particles are distributed in the membranes of polyurethane foam and thereby improve the thermal insulation significantly in window or door frame assembly or other Ausschäumvorgängen.

Embodiments of the invention

Advantageous embodiments of the invention will be explained in more detail with reference to drawing figures and examples.

Show it:

1 a highly simplified, schematic representation of an arrangement of petroleum coke particles in a matrix;

2 a simplified, schematic representation of a fiber-containing insulating mat ( 2A ), an enlarged partial section of the insulating mat ( 2 B ) as well as a detailed representation of the individual connection points of the fibers of the insulating mat ( 2C );

3 a highly simplified, schematic cross-sectional view of a second embodiment of a fiber-containing insulating mat;

4 a greatly simplified, schematic cross-sectional view of a first embodiment of a shaped body;

5 a highly simplified, schematic cross-sectional view of a second embodiment of a shaped body;

6 a highly simplified, schematic cross-sectional view of a third embodiment of a shaped body;

7 a highly simplified, schematic cross-sectional view of a first embodiment of a gypsum board;

8th a highly simplified, schematic cross-sectional view of a second embodiment of a gypsum board;

9 a highly simplified, schematic cross-sectional representation of a petroleum coke particle-coated fiber (single fiber ( 9A )) as well as a filler coated with petroleum coke particles ( 9B ); such as

10 a simplified schematic representation of a spiral jet mill with high-performance air classifier ( 10A ) and a highly simplified, schematic snapshot of the petroleum coke particles containing flow in the spiral jet mill ( 10B ).

According to the invention, petroleum coke particles, in particular particles of calcined petroleum coke, are used to increase the thermal insulation.

Petroleum coke is a residue of petroleum distillation and is produced in so-called crackers. The calcination frees the petroleum coke from volatiles and gives it purity levels of 99% carbon. Petroleum coke can thus be regarded as carbon, but does not belong to the allotropic forms. Calcined petroleum coke is not graphite. He also has no degree of graphitization, since he has no displaceable layers. Also, it can not be counted among amorphous carbons such as soot. For example, petroleum coke has no typical lubricating effect with respect to graphite and only poor electrical and thermal conductivity.

Depending on the production method, anisotropic or isotropic cokes are produced. According to the present invention, isotropic petroleum cokes are preferred. These are usually freed of volatile constituents by heat treatment, in the range of 1,200 ° C., in rotary kilns. This process is also referred to as calcination. Depending on the application, the calcined coke pieces are broken into small pieces or ground to powder in hammer mills. The petroleum cokes are used almost exclusively for the production of electrodes or in the steel industry as a carburizing agent.

According to the present invention, calcined petroleum cokes are ground to platelet-shaped powders. It has been found that these platelet-shaped powder particles particularly improve the thermal insulation of the building material, since they act in the relevant matrix like small, irregular mirrors and the infrared radiation, i. H. Heat or cold radiation, therefore effectively reflect.

For the use of petroleum cokes as infrared blocker particularly isotropic cokes are suitable. to Use as an infrared blocker in addition to the grain size and the grain shape of importance. As already mentioned, a platelet-shaped grain shape shows particularly good thermal insulation values. According to the invention, such preferred grain shapes are made with delaminating mills. Such mills are z. As ball mills or air jet mills, such as. B. spiral jet mills. Spiral jet mills are particularly suitable because they allow the production of a particularly high proportion of platelet-shaped particles with a comparatively low specific surface area. The petroleum cokes according to the invention have a particularly high aspect ratio.

The petroleum coke particles expediently have a specific surface area in the range of 3-50 m ² / g, preferably 3-35 m ² / g, particularly preferably 3-20 m ² / g. In the present invention, aspect ratio means the ratio of the average diameter to the average thickness of the particles.

The petroleum coke may preferably be comminuted in a hot gas jet mill with high performance air classifier to produce the petroleum coke particles having a platy particle shape and a low specific surface area. 10A shows in a simplified representation of the principle of a spiral jet mill with attached air classifier. As gas 20 In this case, highly stressed steam or hot air, preferably from an oil-free screw compressor, can be used. The gas temperature is preferably in the range of 120 ° C to 250 ° C. By suitable adjustment and geometry of the air nozzles and the air classifier (classifying wheel) particles with suitable average particle size can be obtained.

10B shows the tangential inflow of gas 20 via appropriately arranged nozzles 21 for generating a radial current 22 which the particles 1 along the spiral jet mill 19 spirally accelerates, causing the particles 1 be comminuted and slowly depending on their size to the center of the spiral jet mill 19 move. There they are about the air classifier 23 (see. 10A ) discharged on reaching the appropriate grain size. By the application of this particularly delaminating acting milling technique, the platelet-shaped particle shape of petroleum coke particles 1 reached.

Conveniently, the average particle size is in the range of 1 .mu.m to 50 .mu.m, preferably 1 .mu.m to 25 .mu.m, particularly preferably 1 .mu.m to 10 .mu.m. These are preferably used in the context of the present invention.

The petroleum cokes according to the invention have an aspect ratio between 1 and 500, preferably between 5 and 50.

Advantageously, the petroleum coke may be contained in an amount of 0.05 wt .-% - 10 wt .-% based on the finished body or molded body, so that adjusts the correspondingly reduced thermal conductivity.

The thermal conductivity of the building material with petroleum coke compared to a corresponding building material without petroleum coke may be reduced by at least 2.5%, preferably by at least 10%, particularly preferably by at least 20%.

1 shows only in a highly simplified, schematic representation of the arrangement of two platelet-shaped petroleum coke particles 1 as an example of a plurality of corresponding particles in a suitable matrix 15 , Under matrix 15 can z. As a binder, a mass offset or the like can be understood. The petroleum coke particles 1 are randomly oriented and therefore act like small reflection mirrors, the heat and cold jets 3 reflect and thus improve the thermal insulation of the building material.

2A to 2C show the use of petroleum coke particles 1 in a fiber mat 4 , The reference number 5 denotes the respective fibers, e.g. As glass fibers, stone fibers or natural fibers such. B. wood fibers. On one side of the fiber mat 4 is a lamination 16 , z. B. in the form of an aluminum foil provided. The fibers 5 are distributed indiscriminately, the intervening air serves as an isolation agent.

The individual fibers 5 be according to 2 B in the area of their contact points 18 by means of a petroleum coke particle 1 containing binder 2 connected.

2C shows a simplified, exemplary representation of a point of attachment of two fibers 5 that is in a petroleum coke particle 1 containing binder 2 is embedded.

When using mineral fibers, especially glass and / or rock wool, are usually used as a binder 2 Resins, such as As phenolic resins used.

Instead of adding the petroleum coke particles 1 in the binder 2 it is also possible the petroleum coke particles 1 first in a binder 2 or to disperse in a binder solution and then fibers 5 or fiber composites with the dispersion by impregnation, dipping, spraying or the like to coat. A appropriately coated fiber 5 is in the illustration after 9A played.

One on both sides with a petroleum coke particle 1 having layer 6 . 7 coated fiber insulating mat 4 is out 3 seen. The layer 6 respectively. 7 may also be formed by impregnation, dipping, spraying or the like.

For the binder 2 it is preferably a thermosetting or hydraulically curing binder.

Alternatively, as a building material, an insulating mat, insulation board or insulating body on the basis of bonded with binder wood fibers, natural fibers, eg. B. lignocellulosic fibers may be provided. The petroleum coke particles 1 are mixed into the binder and homogeneously distributed there. These are predominantly the following binders: urea-formaldehyde, melamine-urea-formaldehyde, melamine-urea-phenol-formaldehyde, phenol-urea-formaldehyde, phenol-formaldehyde and PMDI resins.

4 shows the building material according to the invention in the form of a molded block 14 in which the petroleum coke particles 1 into the mass of the formstone 14 are embedded. In particular, this type of so-called hydraulically bound stones, such as. As concrete blocks, in which the petroleum coke particles 1 be added directly to the concrete offset, so that the petroleum coke particles 1 into the mass of the formstone 14 are integrated.

Alternatively, with a molded block 14 as he is in 5 shown is the petroleum coke particles 1 including material, in particular a heat-insulating mat or a plurality of petroleum coke particles coated or offset with petroleum coke particles or a petroleum coke particles-containing foam, even within the mold cavity 8th of the formstone 14 are located. At the in 5 illustrated embodiment of the mold cavity 8th completed.

Alternatively, in the embodiment according to 6 only the inner wall of the mold cavity 8th with a petroleum coke particle 1 comprehensive layer provided.

The above embodiments according to the 5 and 6 are particularly suitable for burned stones, such. As bricks, but also for hydraulically bound bricks. To coat the walls of the cavities, a suspension of petroleum coke particles and binder is used.

Conveniently, the petroleum coke particles are metered within the suspension so that no percolation occurs.

In the same way, as in the embodiment according to 7 is shown, petroleum coke particles also in a gypsum board 9 be introduced. The plasterboard 9 includes an outer layer 10 as well as inner layer 11 which is a layer of gypsum 12 mounting. In the shift 12 are the petroleum coke particles 1 in irregular arrangement.

Further, alternatively or in addition to the above configuration, on the outside of the gypsum board 9 an additional layer 13 , the petroleum coke particles 1 contains, be upset (see 8th ).

Petroleum coke particles 1 can in the context of the invention also for the coating of packing 17 For example, from perlite, expanded clay, vermiculite or mica, used as in 9B is shown schematically. Here, the petroleum coke particles become similar to the coating of the fiber 9A by means of a binder 2 applied to the surface of the packing. Such fillers 17 For example, for filling mold cavities within form stones, z. As bricks or mineral bound building blocks used.

Petroleum coke particles 1 it is also possible to add spreadable, fillable or pourable materials.

According to a further embodiment of the present invention, petroleum coke particles are added to foams which are used individually by the user. These are usually foamed by a blowing agent polymers or foams that are formed by reaction gases in the reaction of two-component systems. At z. As foams made of polyurethane, one of the reaction components, the petroleum coke particles. The petroleum coke particles can be mixed into the polyol or isocyanate required for the reaction.

In the case of moisture-reactive polyurethanes (in particular in so-called assembly foams), the petroleum coke particles can also be added directly to the reaction component. When applied from the aerosol can, the petroleum coke particles are distributed in the membranes of the polyurethane foam and thereby improve the thermal insulation in window or Türzargenmontagen or other foaming operations in a significant way.

The use of platelet-shaped petroleum coke particles, in particular from calcined petroleum coke leads to a significant improvement in the Thermal insulation effect with respect to the above building materials. In addition, there is a clear shielding of electromagnetic radiation, so that the building material according to the invention in addition to the efficient thermal insulation also contributes to a reduction of the electromagnetic load (electrosmog). Furthermore, platelet-shaped petroleum coke particles have a synergistic effect with flame retardants, with the result that the amount of flame retardants used can be reduced. The flame retardants are, in particular, organic bromine compounds or ammonium polyphosphate. The invention also provides a reduced dripping behavior in polymers.

LIST OF REFERENCE NUMBERS

1

particle

2

binder

3

Cold / heat radiation

4

Faserdämmmatte

5

fiber

6

layer

7

layer

8th

mold cavity

9

plasterboard

10

outer layer

11

inner layer

12

Layer of plaster

13

additional layer

14

cast stone

15

matrix

16

lamination

17

packing

18

contact point

19

Spiral jet mill

20

gas

21

jet

22

electricity

23

air classifier

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• WO 2008/089085 A1 [0003]
• EP 1749805 [0004]
• WO 2005/120146 [0005]
• DE 202008014415 U1 [0006]
• EP 2028329 A1 [0006]
• DE 19728543 A1 [0007]
• WO 97/45477 [0008]
• EP 0372343 A1 [0009]
• WO 2008/141767 A2 [0010]

Claims (18)

Building material with heat-insulating property, characterized in that the building material particles ( 1 ) of petroleum coke, in particular calcined petroleum coke, and the building material is a non-metallic-inorganic material and / or a natural substance and / or a plastic other than polystyrene. Building material according to claim 1, characterized in that the petroleum coke is formed isotropically. Building material according to at least one of claims 1 or 2, characterized in that the petroleum coke particles ( 1 ) have a platelet-shaped grain shape. Building material according to at least one of the preceding claims, characterized in that the petroleum coke particles ( 1 ) have a specific surface area in the range of 3-50 m ² / g, preferably 3-35 m ² / g, particularly preferably 3-20 m ² / g. Building material according to at least one of the preceding claims, characterized in that the petroleum coke particles ( 1 ) have an aspect ratio of 1-500, preferably 5-50, wherein the aspect ratio is the ratio of the average diameter to the average thickness of the particles ( 1 ). Building material according to at least one of the preceding claims, characterized in that the petroleum coke particles ( 1 ) have an average particle size of 1 .mu.m-50 .mu.m, preferably of 1 .mu.m-10 .mu.m. Building material according to at least one of the preceding claims, characterized in that the petroleum coke particles ( 1 ) are comminuted in a spiral jet mill, preferably a hot gas jet mill. Building material according to claim 7, characterized in that the spiral jet mill has an air classifier. Building material according to at least one of the preceding claims, characterized in that the thermal conductivity of the building material in comparison to a corresponding building material without petroleum coke is reduced by at least 2.5%, preferably by at least 10%, particularly preferably by at least 20%. Building material according to at least one of the preceding claims, characterized in that the petroleum coke is contained in an amount of 0.05 wt .-% - 10 wt .-% based on the total weight of the building material. Building material according to at least one of the preceding claims, characterized in that the building material is a binder ( 2 ) and the petroleum coke particles ( 1 ) in the binder ( 2 ) are distributed. Building material according to at least one of the preceding claims, characterized in that the building material has a coating which petroleum coke particles ( 1 ) contains. Building material according to at least one of the preceding claims, characterized in that the building material is a fired shaped body with mold cavities ( 8th ) and the walls of the mold cavities ( 8th ) at least in part with a petroleum coke particle ( 1 ) are provided coating. Building material according to at least one of the preceding claims, characterized in that it is the building material is a hydraulically bonded molding or a plaster-containing molding. Building material according to at least one of the preceding claims, characterized in that the building material is foamed polymeric material. Building material according to at least one of the preceding claims, characterized in that the building material is a fiber, in particular a mineral fiber, and the fiber is provided with a coating which contains particles ( 1 ) of petroleum coke, in particular calcined petroleum coke. Building material according to at least one of the preceding claims, characterized in that the building material is a composite of individual fibers ( 5 ), which by means of a binder ( 2 ) are bound together and the particles ( 1 ) of petroleum coke, in particular calcined petroleum coke, in the range of the binder ( 2 ) are located. Building material according to at least one of the preceding claims, characterized in that the building material is one with particles ( 1 ) of petroleum coke, in particular calcined petroleum coke, coated packing ( 17 ), in particular packing ( 17 ) made of perlite, expanded clay, vermiculite or mica.

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