GB1585850A - Manufacture of fire protection materials - Google Patents
Manufacture of fire protection materials Download PDFInfo
- Publication number
- GB1585850A GB1585850A GB3389677A GB3389677A GB1585850A GB 1585850 A GB1585850 A GB 1585850A GB 3389677 A GB3389677 A GB 3389677A GB 3389677 A GB3389677 A GB 3389677A GB 1585850 A GB1585850 A GB 1585850A
- Authority
- GB
- United Kingdom
- Prior art keywords
- molding
- coating
- water
- alkali metal
- metal silicate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
- E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
- E04B1/62—Insulation or other protection; Elements or use of specified material therefor
- E04B1/92—Protection against other undesired influences or dangers
- E04B1/94—Protection against other undesired influences or dangers against fire
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
- C04B28/26—Silicates of the alkali metals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B30/00—Compositions for artificial stone, not containing binders
- C04B30/02—Compositions for artificial stone, not containing binders containing fibrous materials
Description
(54) MANUFACTURE OF FIRE PROTECTION MATERIALS
(71) We, BASF AKTIENGESELL
SCHAFT, a German Joint Stock Company of 6700 Ludwigshafen. Federal Republic of
Germany, do hereby declare the invention, for which we pray that a Patent may be granted to us, and the method by which it is to be performed. to be particularly described in an by the following Statement:
The present invention relates to a process for the manufacture of fire protection materials by thermoplastic processing of predried alkali metal silicates having a defined water content.
It is known that moldings, eg. sheets or strips. of alkali metal silicates containing water, when exposed to heat in a fire. form a fine-celled, firm. non-combustible and heat-insulating foam which, due to the foaming pressure developed. is capable of effectively sealing joints. gaps and other openings and passages in building units against the passage of fire and smoke.
German Published Applications DAS 1.169,832, 1.176.516 and 1.471.005 disclose a process for the manufacture of such fire protection sheets. In this process, reinforcing fibers or fabrics are embedded in a cast layer of an alkali metal silicate solution or suspension: the water is then partially removed by heating and the layer consolidated to form a sheet. However, drying of relatively thick sheets is expensive and time-consuming. above all if they are manufactured individually and in large numbers.
In practice. the drying time required for the manufacture of commercial fire protection sheets from alkali metal silicates containing water is at least from 1 to 4 hours even if efficient drying installations are used.
German Laid-Open Application DOS 2.055.283 discloses a process for the manufacture of silicate foams for building elements in which a finelv divided alkali metal silicate. which contains less than 5c' of water, is hvdrated to a water content of from 5 to 30% and is then foamed. An alternative method for the manufcture of silicate foams, in which alkali metal silicate solutions are subjected to controlled dehydration, is described as disadvantageous since it is expensive and leads to non-uniform elimination of water.
We have found the fire protection materials can be manufctured particularly advantageously by first converting an alkali metal silicate solution. bv predrying. into a freeflowing or pourable mass. then molding this mass thermoplasticallv to give the desired molding and coating the molding or the predried mass.
Accordingly. the present invention provides a process for the manufacture of a fire protection material. which comprises the following steps:
A. a liquid alkali metal silicate/water mixture containing from 45 to 95% by weight of water is dried to a water content of from 6 to 40cue by weight,
B. the resulting mass. optionally after being mixed with a reinforcing agent andlor one or more other additives, is converted to the plastic state by heating to from 40 to 100"C.
C. simultaneously or subsequently. the plastic mass is compression-molded and
D. the molding obtained is cooled. in which process either the molding or material from step A or both are provided with a coating.
In this process. the water to be expelled is not removed from the molded articles.
which in most cases have a large surface and are thick, but instead is removed from the fluid solution before molding. Using efficient commercial drying equipment. it is possible to dry alkali metal silicate solutions very rapidly and economicallv to give products which are pourable solids at room temperature and have defined residual water contents. The advantages inherent in the conventional process of manufacture of fire protection sheets, such as easy molding, especially in the case of articles of large surface area, reliable embedding of fillers, fibers or fabrics, and the like, also distinguish the process according to the invention.
The disadvantages of the conventional process, such as the expensive dehydration and consolidation of the moldings, are substantially avoided by carrying out these stages prior to molding.
The starting material is a fluid alkali metal silicate/water mixture containing from 45 to 95, preferably from 50 to 80, % by weight of water. The silicates are preferably sodium, potassium or lithium silicates with a molar ratio M2O:SiO2 of from 1:1 to 1:6, especially from 1:2.5 to 1:4. The aqueous solution is now dried by means of conventional drying equipment, eg. drum dryers, spray dryers, spray towers or vacuum dryers, to a water content of from 6 to 40, preferably of from 15 to 35, % by weight.
The drying is in general carried out at material temperatures below 100"C, because alkali metal silicates which have been dried at higher temperatures in general lose the property of foaming when exposed to a fire, even if they still contain sufficient residual water. However, most drying equipment operates particuarly economically at air temperatures far above 100"C, so that it may at times happen, and is unavoidable, that the material temperature will on one or more occasions briefly, or even for a prolonged period, exceed 100"C. In such cases the moldings obtained after thermoplastic processing should be stored, after shaping and any coating process, but before further processing, for several days, preferably for from 2 to 10 days, at room temperature.This causes the moldings to recover their ability to foam in the event of a fire.
On drying the alkali metal silicate solution, a pulverulent flowable or pourable mass is obtained, which preferably consists of particles having a mean diameter of from 0.01 to 5.0 more preferably of from 0.05 to 1.0, mm. In general, if conventional dryers, eg. spray dryers, are used, the powder obtained has a relatively broad particle size spectrum, ie. in addition to numerous fine particles some coarse constituents are also obtained. This is often advantageous since on pouring the powder a denser packing of the particles is achieved, and the latter can then be compressed more easily during molding. The particle size distribution can be broadened further by using special nozzle designs of the spray equipment to produce droplets of different size, leading to particles of different size being obtained after drying.Because of the varying residence time in the dryer, the small particles are dried more extensively than the large; accordingly, the water content data represent mean values. This mixture of coarser and finer, moister and drier, particles is surprisingly free-flowing and shows no tendency to cake in reservoirs and metering vessels. The residual water content of the mixture can, if necessary, readily be corrected by adding traces of water or by spraying with steam, without essentially detracting from the free-flowing character of the product. By means of this measre, it is possible, where necessary, to achieve better cohesion during molding or easier embedding of fibrous materials.
In spite of the use of particles with different water contents and hence different expandability, the process according to the invention gives flame protection materials which, in the event of a fire, give a homogeneous, fire-retardant foam.
In order to shield the fire protection materials from the action of water and CO2, it is advantageous to provide the particles manufactured in stage A with alkaliresistant coatings. Particularly suitable coatings of this type are epoxy resins which comprise a mixture of polyepoxides and polyamine curing agents; polyurethane surface coatings based on polyols and polyisocyanates; aqueous synthetic resin dispersions based on butadiene polymers or isoprene polymers; and solutions of waxes especially paraffin waxes and polyethylene waxes, in organic solvents.
The coatings may be applied to the particles in diverse ways. The predried alkali metal silicate particles can be coated with a dispersion or solution of the coating agent, eg. by bringing them into thorough contact in conventional mixing equipment.
Alternatively, the particles can be embedded in the liquid coating agent, but in that case larger amounts of the coating agent are required. The amount of coating agent (expressed as solids) is in general from 0.1 to 10, especially from 1 to 5, % by weight, based on the coated particles.
The mass which is produced in process stage A and which is preferably free-flowing or pourable and optionally provided with a coating is mixed in stage B, if desired, with a reinforcing agent, with or without one or more other additives, and is converted simultaneously or subsequently to the plastic state by heating to from 40 to 110 C, preferably from 70 to 100"C. Reinforcing agents which may be incorporated include in particular textile fibers, metal fibers or mineral fibers, fabrics, mats or nets. In this way, mechanically particularly resistant moldings are obtained if the reinforcing agents are located in one place, foaming in the event of a fire takes place in a defined direction at right angles to this plane.It is particularly preferred to incorporate glass fibers, in amounts of from 1 to 25, preferably from 2 to 10, % by weight, based on the total mixture. In addition, conventional dyes, pigments, foaming assistants and wetting agents may be incorporated to achieve special effects, and carbohydrates, which on heating form a carbon skeleton, may be added to raise the melting point.
Plasticization can be effected on various equipment; preferably, the pulverulent mass is poured onto a continuous moving steel belt and is heated thereon by means of radiation heating or contact heating or by exposure to hot air. However, heating can also be effected whilst the material is exposed to pressure, simultaneously with the molding process of stage C, for example on heated rolls or in extruders.
The plastic mass can be molded by means of all conventional molding equipment, such as stamping presses or sheet presses, roller presses, calenders, mills with smooth or profiled rolls, or extruders. Moldings of any desired shape and size may be produced, eg.
sheets, continuous strips or web-like profiles. Preferably, webs from 0.5 to 10 mm thick are manufactured and these may subsequently be cut lengthwise into strips which are from 1 to 100 cm wide, preferably from 2 to 10 cm wide.
The moldings manufactured according to the invention require at most a slight subsequent drying, if any, and are then cooled.
When the particles from step A have not been provided with a coating, and preferably even when they have the moldings are provided, desirably immediately after cooling, with a coating to protect them against mechanical damage and above all against loss of water and against penetration of water and of CO2. Suitable coatings are plastic films or metal foils, eg. aluminium foils. However, the moldings can also be coated with finishes based on polyvinyl chloride, epoxy resins or polyurethanes, which, where appropriafte, can subsequently be cured. The moldings can be provided with a durable and complte coating by dipping, spraying or brushing. This can be done in a simple manner directly after molding, so that the heat communicated to the moldings for the purpose of the molding process can be utilized to cure the surface coating.At high throughputs, in particular, this acceleration of curing saves costs.
In the Examples which follow, parts and percentages are by weight.
Example 1
A sodium silicate solution containing about 65% of water and having a molar ratio of Na2O:SïO2 of 1:3.3 is sprayed in a spray dryer and dried at an air temperature of about llO"C. The selected residual water content is 34% by weight. The pulverulent and granular mixture, with a mean particle diameter of 0.2 mm, is applied, by means of a hopper provided with a comb-like distributor bar, onto a steel belt, to form 6 separate parallel continuous strips of powder.
These strips are heated to a material temperature of about 95"C by infrared radiators which radiate vertically downwards. The steel belt is passed through a mill with a smooth lower roll, whilst the upper roll is provided with 6 wedge-shaped grooves which are from 25 to 27 mm wide and 3 mm deep. The grooves press and mold the pulverulent heated strands into continuous profiles of size 25 x 3 mm. The strands are detached from the steel bolt by a downward change of direction of the latter and are fed by means of a roller track into-a second mill, the grooves of which bring the strands to their final size of 25 x 2.5 mm.
Then the strands are cooled to room temperature. The water content of the strands is now 33% by weight. The 6 strands then pass through a dipping bath containing a polyurethane surface coating, which is applied as a layer about 0.1 mm thick and is crosslinked in a downstram curing tunnel.
The strands are wound up, cut to length and packaged.
Example 2
Commercial sodium silicate solution (containing 65% of water) is sprayed at an air temperature of about 110 C in a spray dryer and converted to a mixture of fine and coarse particles having a residual water content of 36%. The material is cooled to room temperature and then mixed. in a forced mixer, with glass fibers chopped to an 8 mm length, in the ratio of 20:1.
The mold of a compression molding press is first filled to the extent of about 50% with his mixture by means of a loading slide, the mold is lowered into the final position, and a mesh of 0.5 mm thick wire with a mesh size of 15 x 15 mm, the mesh having been cut to the appropriate size by hand and premolded into a semi-cylindrical shape, is inserted.
The mold is completely filled by means of a loading slide and the pressing process is carried out in the conventional manner by pre-pressing, breathing and after-pressing.
The top and bottom halves of the mold are heated (material temperatures 95"C). The total pressing time depends on the size and particularly the thickness of the press molding which in the present case is a pipe covering reinforced with glass fibers and wire mesh and has a length of 100 mm. a diameter of 100 mm and a wall thickness of 5 mm.
Pipe coverings thus obtained are passed, after cooling, on frames, through a dipping bath in order to apply a surface coating based on an epoxy resin; after the coating has cured tack-free, the moldings are sorted and packaged.
Example 3
Granular and pulverulent alkali metal silicate prepared as described in Example 1 is mixed with chopped glass fiber (6 mm length) in a mixer and the mixture is applied as a flat strand onto a steel belt, where it is heated from above and below to a material temperature of 95"C and pre-compressed by means of a smooth roll. After leaving the steel belt, the strand passes through a profiling mill in whcih 7 continuous stripshaped profiles are formed simultaneously.
After cooling to room temperature, they pass through a dipping bath where the surface is sealed with a polyurethane finish, after which they pass through a curing tunnel and are wound up.
Example 4
A composition prepared as described in
Example 1 and having a residual water content of 34% is fed by means of a bucket wheel to a profiling mill resembling a briquetting press, on which the material, which is at a temperature of 90"C, is converted to saddle-shaped moldings of size 30 x 15 x 2 mm which, in the form of a loose packing, resembling Raschig rings, permit ready passage of air through the packing whilst, on exposure to high temperatures, eg. in the event of a fire, they foam up to fill the volume occupied by the packing. The saddle-shaped moldings are sealed over their entire surface by means of a polyurethane finish in a fluidized bed, in order to protect them against the action of water or CO2.
Example 5
100 parts of granular sodium silicate containing water, the particle size of the material being about 1 mm 8 and the residual water content being 25%, are mixed with 5 parts of 30 mm long glass fibers and 3 parts of a polyurethane surface coating (based on a polyether-polyol and polyisocyanate), and are molded in a press at 80"C for 20 minutes to give a sheet of size 400 x 100 x 8 mm. In the course of the molding process, the polyurethane surface coating cures. After cooling to room temperature, the foamability of the sheet is tested in a muffle oven by heating at 500"C.
The size of the foamed sheet is 500 x 120 x 40 mm.
Example 6
Sodium silicate, the particle size of the material being from 2 to 4 mm 8 and the residual water content being 28%, is mixed with 1% of an epoxy resin (based on bisphenol Alepichlorohydrin + a polyamine curing agent) and after precuring for 50 minutes the material is molded under slight pressure in a platen press, the platens being at 80"C. On subsequently storing the molding in water, no alkaline reaction is found after 24 hours.
WHAT WE CLAIM IS:
1. A process for the manufacture of a fire protection material, which comprises the following steps:
A. a liquid alkali metal silicate/water mixture containing from 45 to 95% by weight of water is dried to a water content of from 6 to 40% by weight,
B. the resulting material, optionally after beong mixed with a reinforcing agent and/or one or more other additives, is converted to the plastic state by heating to from 40 to 100"C, C. simultaneously or subsequently the plastic mass is compression molded, and
D. the molding obtained is cooled, in which process either the molding or the material from step A or both are provided with a coating.
2. A process as claimed in Claim 1, in which the molding is provided with a coating after it has cooled but the material from step
A is not provided with a coating.
3. A process as claimed in Claim 1, in which the material produced in stage A is provided with an alkali-resistant coating.
4. A process as claimed in any of Claims 1 to 3, in which the fluid alkali metal silicate/water mixture is dried at a material temperature below 100"C.
5. A process as claimed in any of Claims 1 to 3, in which a material temperature of 100"C is exceeded on one or more occasions whilst drying the fluid alkali metal silicate/ water mixture, and the finished molding, after molding and any coating process is stored for from 2 to 10 days at room temperature before being processed further.
6. A process as claimed in any of Claims 1 to 5, in which the material produced after drying in stage A is free-flowing or pourable and consists of fine particles having a means diameter of from 0.01 to 5.0 mm.
7. A process as claimed in any of Claims 1 to 6, in which in stage B reinforcement selected from metal, textile and mineral fibers, fabrics, mats and nets is incorporated into the material,.
8. A process as claimed in Claim 7, in which the reinforcement is glass fibers in an amount of from 1 to 25% by weight based on the total mixture.
9. A process s claimed in any of Claims 1 to 8, in which the plastic mass is molded in stage C to give a web which is from 0.5 to 10 mm thick, and which is optionally then cut lengthwise into strips which are from 2 to
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (13)
- **WARNING** start of CLMS field may overlap end of DESC **.bath in order to apply a surface coating based on an epoxy resin; after the coating has cured tack-free, the moldings are sorted and packaged.Example 3 Granular and pulverulent alkali metal silicate prepared as described in Example 1 is mixed with chopped glass fiber (6 mm length) in a mixer and the mixture is applied as a flat strand onto a steel belt, where it is heated from above and below to a material temperature of 95"C and pre-compressed by means of a smooth roll. After leaving the steel belt, the strand passes through a profiling mill in whcih 7 continuous stripshaped profiles are formed simultaneously.After cooling to room temperature, they pass through a dipping bath where the surface is sealed with a polyurethane finish, after which they pass through a curing tunnel and are wound up.Example 4 A composition prepared as described in Example 1 and having a residual water content of 34% is fed by means of a bucket wheel to a profiling mill resembling a briquetting press, on which the material, which is at a temperature of 90"C, is converted to saddle-shaped moldings of size 30 x 15 x 2 mm which, in the form of a loose packing, resembling Raschig rings, permit ready passage of air through the packing whilst, on exposure to high temperatures, eg. in the event of a fire, they foam up to fill the volume occupied by the packing. The saddle-shaped moldings are sealed over their entire surface by means of a polyurethane finish in a fluidized bed, in order to protect them against the action of water or CO2.Example 5100 parts of granular sodium silicate containing water, the particle size of the material being about 1 mm 8 and the residual water content being 25%, are mixed with 5 parts of 30 mm long glass fibers and 3 parts of a polyurethane surface coating (based on a polyether-polyol and polyisocyanate), and are molded in a press at 80"C for 20 minutes to give a sheet of size 400 x 100 x 8 mm. In the course of the molding process, the polyurethane surface coating cures. After cooling to room temperature, the foamability of the sheet is tested in a muffle oven by heating at 500"C.The size of the foamed sheet is 500 x 120 x 40 mm.Example 6 Sodium silicate, the particle size of the material being from 2 to 4 mm 8 and the residual water content being 28%, is mixed with 1% of an epoxy resin (based on bisphenol Alepichlorohydrin + a polyamine curing agent) and after precuring for 50 minutes the material is molded under slight pressure in a platen press, the platens being at 80"C. On subsequently storing the molding in water, no alkaline reaction is found after 24 hours.WHAT WE CLAIM IS: 1. A process for the manufacture of a fire protection material, which comprises the following steps: A. a liquid alkali metal silicate/water mixture containing from 45 to 95% by weight of water is dried to a water content of from 6 to 40% by weight, B. the resulting material, optionally after beong mixed with a reinforcing agent and/or one or more other additives, is converted to the plastic state by heating to from 40 to 100"C, C. simultaneously or subsequently the plastic mass is compression molded, and D. the molding obtained is cooled, in which process either the molding or the material from step A or both are provided with a coating.
- 2. A process as claimed in Claim 1, in which the molding is provided with a coating after it has cooled but the material from step A is not provided with a coating.
- 3. A process as claimed in Claim 1, in which the material produced in stage A is provided with an alkali-resistant coating.
- 4. A process as claimed in any of Claims 1 to 3, in which the fluid alkali metal silicate/water mixture is dried at a material temperature below 100"C.
- 5. A process as claimed in any of Claims 1 to 3, in which a material temperature of 100"C is exceeded on one or more occasions whilst drying the fluid alkali metal silicate/ water mixture, and the finished molding, after molding and any coating process is stored for from 2 to 10 days at room temperature before being processed further.
- 6. A process as claimed in any of Claims 1 to 5, in which the material produced after drying in stage A is free-flowing or pourable and consists of fine particles having a means diameter of from 0.01 to 5.0 mm.
- 7. A process as claimed in any of Claims 1 to 6, in which in stage B reinforcement selected from metal, textile and mineral fibers, fabrics, mats and nets is incorporated into the material,.
- 8. A process as claimed in Claim 7, in which the reinforcement is glass fibers in an amount of from 1 to 25% by weight based on the total mixture.
- 9. A process s claimed in any of Claims 1 to 8, in which the plastic mass is molded in stage C to give a web which is from 0.5 to 10 mm thick, and which is optionally then cut lengthwise into strips which are from 2 to100 cm wide.
- 10. A process as claimed in any of Claims 1 to 9, in which the molding is coated with a curable finish after it has cooled.
- 11. A process as claimed in any of Claims 1 to 10, in which the alkali metal silicate/water mixture initially contains 50 to 80% by weight of water and is dried to a water content of 15 to 35% by weight in stage A, the alkali metal silicate being sodium potassium or lithium silicate with a molar ratio of alkali metal oxide: silica of from 1:1 to 1:6.
- 12. A process for the manufacture of a fire protection material carried out substantially as described in any of the foregoing Examples.
- 13. Fire protection materials when manufactured by a process as claimed in any of Claims 1 to 12.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2636430A DE2636430B2 (en) | 1976-08-13 | 1976-08-13 | Process for the production of fire protection materials |
DE19762650827 DE2650827A1 (en) | 1976-11-06 | 1976-11-06 | Fire-resistant material mfr. - from alkali silicate soln. by partial drying and moulding plastically and heating |
Publications (1)
Publication Number | Publication Date |
---|---|
GB1585850A true GB1585850A (en) | 1981-03-11 |
Family
ID=25770809
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB3389677A Expired GB1585850A (en) | 1976-08-13 | 1977-08-12 | Manufacture of fire protection materials |
Country Status (3)
Country | Link |
---|---|
JP (1) | JPS5323324A (en) |
FR (1) | FR2361318A1 (en) |
GB (1) | GB1585850A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2189426A (en) * | 1986-04-23 | 1987-10-28 | Hackett James W | Forming an article of ceramics material |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE898845A (en) * | 1984-02-06 | 1984-08-06 | Drim Ltd | ELEMENT IN AN INTUMESCENT REFRACTORY COMPOSITION AND PARTICULAR PROCESS FOR PREPARING THE SAME |
JPH03106335U (en) * | 1990-02-14 | 1991-11-01 | ||
JP2003081679A (en) * | 2001-09-05 | 2003-03-19 | Keiichi Katsuyo | Moisture absorbing and desorbing material and method of producing the same |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL275385A (en) * | 1961-03-01 | |||
FR1320981A (en) * | 1961-03-01 | 1963-03-15 | Basf Ag | Protective materials against fire in the form of plates or other elements obtained therefrom |
FR1417893A (en) * | 1964-12-21 | 1965-11-12 | Basf Ag | Process for improving the flame retardant properties of building panels |
US3912481A (en) * | 1974-02-25 | 1975-10-14 | Corning Glass Works | Method for making alkali metal silicate thermoplastic materials |
-
1977
- 1977-08-10 FR FR7724640A patent/FR2361318A1/en active Granted
- 1977-08-12 GB GB3389677A patent/GB1585850A/en not_active Expired
- 1977-08-12 JP JP9622477A patent/JPS5323324A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2189426A (en) * | 1986-04-23 | 1987-10-28 | Hackett James W | Forming an article of ceramics material |
GB2189426B (en) * | 1986-04-23 | 1989-11-29 | Hackett James W | A method of forming a lamp base. |
Also Published As
Publication number | Publication date |
---|---|
FR2361318A1 (en) | 1978-03-10 |
FR2361318B1 (en) | 1984-06-22 |
JPS5323324A (en) | 1978-03-03 |
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Legal Events
Date | Code | Title | Description |
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PS | Patent sealed | ||
PCNP | Patent ceased through non-payment of renewal fee |