CA1214914A - Structural units and method for forming same - Google Patents
Structural units and method for forming sameInfo
- Publication number
- CA1214914A CA1214914A CA000416219A CA416219A CA1214914A CA 1214914 A CA1214914 A CA 1214914A CA 000416219 A CA000416219 A CA 000416219A CA 416219 A CA416219 A CA 416219A CA 1214914 A CA1214914 A CA 1214914A
- Authority
- CA
- Canada
- Prior art keywords
- layer
- concrete
- epoxy resin
- moulded
- shell
- 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
- E04G—SCAFFOLDING; FORMS; SHUTTERING; BUILDING IMPLEMENTS OR AIDS, OR THEIR USE; HANDLING BUILDING MATERIALS ON THE SITE; REPAIRING, BREAKING-UP OR OTHER WORK ON EXISTING BUILDINGS
- E04G23/00—Working measures on existing buildings
- E04G23/02—Repairing, e.g. filling cracks; Restoring; Altering; Enlarging
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B19/00—Machines or methods for applying the material to surfaces to form a permanent layer thereon
- B28B19/0046—Machines or methods for applying the material to surfaces to form a permanent layer thereon to plastics
Landscapes
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Ceramic Engineering (AREA)
- Laminated Bodies (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
There is disclosed a moulded shell unit com-prising an outer and an inner layer, the outer layer consisting of a cured epoxy resin and the inner layer consisting of a layer of aggregates partially embedded in the inner face of the cured epoxy resin. The layer of aggregates may also be coated with a layer of fiber reinforced concrete. The shell units of the present invention are suitable to mould concrete units protected by epoxy resin such as tiles, steps or for repairing concrete units such as supports for bridges.
There is disclosed a moulded shell unit com-prising an outer and an inner layer, the outer layer consisting of a cured epoxy resin and the inner layer consisting of a layer of aggregates partially embedded in the inner face of the cured epoxy resin. The layer of aggregates may also be coated with a layer of fiber reinforced concrete. The shell units of the present invention are suitable to mould concrete units protected by epoxy resin such as tiles, steps or for repairing concrete units such as supports for bridges.
Description
BACKGROUND OF THE INVENTION
Moulded concrete units have been put to differ-ent uses because of their relative economical character.
Of particular interest are concrete units used as security bar.riers for roads or as retaining walls on bridges or overpasses, supporting columns for bridges, steps, balconies, building beams and columns, septic tanks, park benches and tables, burial vaults and the like. Unfortunately, such concrete units have a tendency to deteriorate when used in climates subject to cyclical freezing and thawiny such as roads which are frequently sprayed with chemicals such as calcium chloride ~o cause melting of ice formed on the roads and also deterioration due to aggressive attack of numerous chemical agents such as acids, sulphates and other mate-rials which are deleterious to Portland cement concrete.
In order to overcome such deterioration due to the elements such as freezing and thawing and to contact with chemicals, it has been proposed to protect the exposed surfaces of concrete moulded units with a variety of plastic resinous components. Such a method for coating a concrete moulded unit has been proposed in U.S.P. 3,619,457, W. Chandler, inventor, where a mould, coated with. a parting agent coating, is coated with a plastic resinous component. There is then applied to the plastic resinous component an adhesive bond.ing coating and, before the complet~ curing of the adhesive bonding coating, a concrete rnix is poured into the mould whereby a chemical bond is established betw~en the adhesive bonding coating and the cement mix whi].e curing.
Unfortunately, since there is always a certain amount of retraction (shrinkage~ of the cement mi~ upon setting, there is less than adequate bond be-tween the adhesive coating w.ith the walls of the moulded units which are not horizontal, the concrete mix and the plastic resinous coating so that such moulded units are not suitable for their intended purposes. A further disadvantage of the Chandler procedure is that all units must be moulded within the plant so that transportation of the larger and heavier moulded units is required from the moulding plant to the site of use. A further disad-vantage of the Chandler procedure is that the curing of the adhesive resinous bonding coating and of the con-crete must take place at the same time. Finally, it has been found that the Chandler procedure is not suitable when vertical, inclined or curved walls are present since the adhesive resinous bonding coating has a tendency to run along the vertical walls in the moulding frame and as a result there is a lack of adhesive resinous bonding coating,resulting in th~ absence of adequate bonding between the inner concrete layer and the outer plastic resinous coating~
It would therefore appear desirable if a method could be devised which would resolve the ~ `
~2~
-- 3 ~
drawbacks of the above Chandler procedure relating to an inadequate bond between the outer plastic resinous coating and the inner concrete layer.
It would also appear desirable if a way could be devised whereby moulds of resinous components could be made in a moulding plant and then transported, when large units are required, ~o the site where concrete can be poured into the moulds, thus avoiding the drawbacks of transporting large and heavy moulded concrete units.
10 SUMMARY OF T~E INVENTION
In accordance with the present invention, there is provided a moulded shell unit comprising an outer layer of cured epoxy resin having its correspond-ing inner fac~ bonded to a layer of aggregates embedded in the cured epoxy resinO
In a further aspect of the present invention, there is provided a rigid moulded shell unit comprising an outer layer of cured epoxy resin having a layer of aggregates partially embedded in the inner face of the cured epoxy resin and partially embedded in a layer of cured fiber reinforced concrete.
Also in accordance with the present invention the cement concrete can be poured into any of the moulded shell units of the present invention and af~er the concrete is cured there is provided a moulded concrete unit having part of its outside surface pro-tected with a rigid, cured epoxy resin shell.
The cured epoxy shell units comprising an outer layer of cured epoxy resln and an inner layer of aggregates embedded therein are suitable for receiving Portland cemen~ concrete to provide epoxy resin moulded units which can be manufactured in a concrete manu-facturing plant and the units can then be readily trans-ported for use to any site.
On the other hand, when the moulded units are very large and too heavy to transport if filled with concrete, i~ is preferable to transport the large moulded units of the present invention to the site of use. In this case, the shell units comprise an outer layer of cured epoxy resin, an intermediate layer of aggregates partially embedded in the inner surface of the cured epoxy resin layer and partially embedded in the inner face of a cured layer of cured fiber-reinforced concrete thus providing a shell unit having sufficient rigidity for transportation to the re~uired site. Such reinforced units are suitable for repairing concrete structural units such as security barriers for roads, retaining walls on bridges, overpasses, support-ing columns for bridges or for constructing building beams or columns on site. The repair of damaged concrete structural units involves removal o~ the damaged concrete, cleaning of any exposed reinforcing steel when present, placing the shell unit over concrete structural unit and causing it to adhere ";
thereto. This can be done by means of a bonding agent when the concrete structural unit is small or by pouring fluid concrete b~tween the shell unit and the concrete structural unit whereby curing of the aaded concrete will bind the shell unit to the structural unit.
The present invention also comprises a method for moulding a shell unit which comprises applying an epoxy resin mix to the inner wall or walls of a shaping mould, and before the cuxing is complete, spraying or coating the epoxy resin layer with a layer of aggre-gates. When the ~hickness of the epoxy layer is suf-ficient to provide sufficient rigidity, the shell can be readily removed from the mould. On the other hand, when the epoxy layer is so thin that the shell cannot be removed from the mould, it is then preferable to pour the concrete in the shell unit and after curing of the concrete the whole unit is then removed from the shell thus providing a moulded concrete shape having at least one face coated and thus protected wi$h an epoxy resin.
Also, in a further aspect of the present invention, the layer of aggregate partially embedded in the cured epoxy resin layer can be sprayed with a thin layer of fiber reinforced concrete which will provide the required rigidity and after allowing the reinforced concrete to set, the moulded shsll is removed from the shaping mould and can then be transported to a building site so that concxete may be poured in the moulded shell, thus ~2~
avoiding the transportation of large moulded epoxy resin coated concrete units.
In a further aspect, the mould~ after the spraying or coating of the aggregate and after the epoxy resin is cured, can be filled at any time with cement concrete and, after allowing the unit to set/ the epoxy coated concrete unit is removed from the shaping mould giving a finished concrete unit having at least one face coated with an epoxy resin and the unit can then be transported ~o a building site for installation.
Furthermore, it has been found that the method of the present invention is sui~able for moulding shapes having a vertical, inclined, horizontal or curved surface, thus providing a moulded cement concrete unit of the desired shape and coated ox protected with an outer rigid epoxy resin shell.
DETAILED DESCRIPTION OF THE INVENTION
-In its broadest aspect, the moulded shell units of the present invention are prepared by a method 2Q which comprises applying a layer of epoxy resin to at least one inner surface of a shaping mould which is non~
bonding to epoxy resins, coating the uncured epoxy resin surface with a layer of aggregates and, after allowing the epoxy resin to cure, removing the moulded epoxy resin shell having aggregates embedded in its inner surface. The moulded shPll can then be used to prepare finished concrete products having part of the outside surfaces coated with epoxy resin by pouring concrete in the shell and allowing the concrete to cure whereby said cured concrete will be mechanically bonded with the aygregates which are partially embedded in the cured epoxy resin.
Where it is desired to mould larger unit, it is necessary to provide a moulded shell having suffi-cient rigidity for transportation to the site and suf--ficient resistance to be used as a mould. Accordingly, the method comprises the further step of spraying onto the inner aggregate layer of the moulded shell previ-ously obtained with a lay~r of fiber reinforced concrete which mechanically binds with the layer of aggregates and, after curing said fiber reinforced concrete layer~
the moulded shell unit, after removal from the shaping mould, has sufficient strength and rigidity to be trans-ported to a desired site where concrete will be poured into the unit.
THE MOULDING SURFACE
An important feature of the present invention is the selection of a moulding surface or a mould which is non-bonding to epoxy resins thus avoiding the use of a parting layer required to be applied to the moulding surface or mould in prior art procedures.
In accordance with -the present invention, the shaping mould is made from a material which is itself non-bonding to epoxy resins~ Thus, the shaping mould can be a moulded shape of polyethylene, polypropylene or Teflon and the like. If desired, patterns can be present in the original mould so that moulds which are non-bonding to epoxy resins will be obtained with corre~
sponding patterns or designs thus eventually providing epoxy resin shellshaving the corresponding patterns or designs on their outer surface.
It is also possible to use an ordinary mould, such as wood, and line same with a plastic sheet of a material which is non-bonding to epoxy resins such as polyethylene, polypropylene, Teflon or the like. In this case the plastic sheet can readily be peeled from the cured epoxy resin shell after its removal from the shaping mould.
It will now be appreciated that in previous procedures the moulding surface was coated with a parting or demoulding agent such as polyvinylacetate, waxes or oils to prevent adhesion of the resin layer to the mould surface. In practice this procedure usually led to a mould which could not be readily reused without prior preparation. Furthermore, the moulding surface required elaborate preparation to insure proper and even application of the parting layer to avoid bonding of the epoxy resin layer to the moulding surface r~sulting either in a damaged moulded unit or damaged moulding surface or both. Accordingly, all the undesirable features are eliminated by using the novel moulding surface o~ the present invention.
THE EPOXY RES I N
The epoxy resin is applied ayainst the mould surface which is non-binding to epoxy resin in any suitable manner, such as, by spray, coating with a trowel, a brush or the like.
The thickness of the epoxy resin layer in general can vary from 0.1 mm to 10 mm but in some cases a thick~r coating may be required such as in cases where the epoxy resin layer will b~ subjected to severe abrasive conditions such as road markers where the epoxy layer may be as much as 1 to 1.5 cm in thickness. In many cases, ~he thickness of the epoxy resin layer will be dictated by economical factors, appreciating the cost of epoxy resins, and the intended use of the moulded units~
As fax as the epoxy resin, there is a vast selection available extending from low viscosity to high viscosity. When using a high viscosity, usually one coat is sufficient while when usiny a low viscosity epoxy resin, it is preferable to allow the first coat to cure and then apply a second coat and in some cases, when needed a third coat of low viscosity or even of high viscosity epoxy resin.
Epoxy resins constitute a well defined class of binding resins and are characterized by the opening of epoxy groups in the polymerization process.
~2~
A general description of the preparation o these epoxy resins is presented in the Encyclopedia of Polymer Science and Technology, page 209-271, volume 6, Intersciences Publishers, NYC, 1967. Another reference is "Hand~ook of Epoxy Resins" by H. Lee and K. Neville, McGraw Hill Book Co., Inc., 1967.
The epoxy resins used in accordance with the present invention are prepared from saturated polyhydric alcohols and phenols which contain no carbon to carbon unsaturation other than that which is present in the aromatic ring.
By the epoxy equivalency, reference is made the average number of 1,2-epoxy groups o (C~I2-C ) contained in the average molecule of the ether.
A preferred group of epoxy ethers for use in the invention is prepared by reacting a dihydric phenol with epichlorhydrin in alkaline solution. There products are of resinous character and frequently are solid materials at normal temperature ~20-30C~. Any of the various dihydric phenols are used in preparing these glycidyl ethers, including mononuclear phenols like resorcinol, catechol, hydroquinone, etc., or polynuclear phenols like bis-~4-hydroxyphenol)-2,2-propane ~bis-phenol A), 4,4'-dihydroxy benzophenone, bis-(4-hydroxy-phenyl)-l,l-ethane, bis-(4-hydroxyphenyl)-1,1-iso-butane, bis-(4-hydroxyphenyl)-2,2-butane, bic-(hydroxy-
Moulded concrete units have been put to differ-ent uses because of their relative economical character.
Of particular interest are concrete units used as security bar.riers for roads or as retaining walls on bridges or overpasses, supporting columns for bridges, steps, balconies, building beams and columns, septic tanks, park benches and tables, burial vaults and the like. Unfortunately, such concrete units have a tendency to deteriorate when used in climates subject to cyclical freezing and thawiny such as roads which are frequently sprayed with chemicals such as calcium chloride ~o cause melting of ice formed on the roads and also deterioration due to aggressive attack of numerous chemical agents such as acids, sulphates and other mate-rials which are deleterious to Portland cement concrete.
In order to overcome such deterioration due to the elements such as freezing and thawing and to contact with chemicals, it has been proposed to protect the exposed surfaces of concrete moulded units with a variety of plastic resinous components. Such a method for coating a concrete moulded unit has been proposed in U.S.P. 3,619,457, W. Chandler, inventor, where a mould, coated with. a parting agent coating, is coated with a plastic resinous component. There is then applied to the plastic resinous component an adhesive bond.ing coating and, before the complet~ curing of the adhesive bonding coating, a concrete rnix is poured into the mould whereby a chemical bond is established betw~en the adhesive bonding coating and the cement mix whi].e curing.
Unfortunately, since there is always a certain amount of retraction (shrinkage~ of the cement mi~ upon setting, there is less than adequate bond be-tween the adhesive coating w.ith the walls of the moulded units which are not horizontal, the concrete mix and the plastic resinous coating so that such moulded units are not suitable for their intended purposes. A further disadvantage of the Chandler procedure is that all units must be moulded within the plant so that transportation of the larger and heavier moulded units is required from the moulding plant to the site of use. A further disad-vantage of the Chandler procedure is that the curing of the adhesive resinous bonding coating and of the con-crete must take place at the same time. Finally, it has been found that the Chandler procedure is not suitable when vertical, inclined or curved walls are present since the adhesive resinous bonding coating has a tendency to run along the vertical walls in the moulding frame and as a result there is a lack of adhesive resinous bonding coating,resulting in th~ absence of adequate bonding between the inner concrete layer and the outer plastic resinous coating~
It would therefore appear desirable if a method could be devised which would resolve the ~ `
~2~
-- 3 ~
drawbacks of the above Chandler procedure relating to an inadequate bond between the outer plastic resinous coating and the inner concrete layer.
It would also appear desirable if a way could be devised whereby moulds of resinous components could be made in a moulding plant and then transported, when large units are required, ~o the site where concrete can be poured into the moulds, thus avoiding the drawbacks of transporting large and heavy moulded concrete units.
10 SUMMARY OF T~E INVENTION
In accordance with the present invention, there is provided a moulded shell unit comprising an outer layer of cured epoxy resin having its correspond-ing inner fac~ bonded to a layer of aggregates embedded in the cured epoxy resinO
In a further aspect of the present invention, there is provided a rigid moulded shell unit comprising an outer layer of cured epoxy resin having a layer of aggregates partially embedded in the inner face of the cured epoxy resin and partially embedded in a layer of cured fiber reinforced concrete.
Also in accordance with the present invention the cement concrete can be poured into any of the moulded shell units of the present invention and af~er the concrete is cured there is provided a moulded concrete unit having part of its outside surface pro-tected with a rigid, cured epoxy resin shell.
The cured epoxy shell units comprising an outer layer of cured epoxy resln and an inner layer of aggregates embedded therein are suitable for receiving Portland cemen~ concrete to provide epoxy resin moulded units which can be manufactured in a concrete manu-facturing plant and the units can then be readily trans-ported for use to any site.
On the other hand, when the moulded units are very large and too heavy to transport if filled with concrete, i~ is preferable to transport the large moulded units of the present invention to the site of use. In this case, the shell units comprise an outer layer of cured epoxy resin, an intermediate layer of aggregates partially embedded in the inner surface of the cured epoxy resin layer and partially embedded in the inner face of a cured layer of cured fiber-reinforced concrete thus providing a shell unit having sufficient rigidity for transportation to the re~uired site. Such reinforced units are suitable for repairing concrete structural units such as security barriers for roads, retaining walls on bridges, overpasses, support-ing columns for bridges or for constructing building beams or columns on site. The repair of damaged concrete structural units involves removal o~ the damaged concrete, cleaning of any exposed reinforcing steel when present, placing the shell unit over concrete structural unit and causing it to adhere ";
thereto. This can be done by means of a bonding agent when the concrete structural unit is small or by pouring fluid concrete b~tween the shell unit and the concrete structural unit whereby curing of the aaded concrete will bind the shell unit to the structural unit.
The present invention also comprises a method for moulding a shell unit which comprises applying an epoxy resin mix to the inner wall or walls of a shaping mould, and before the cuxing is complete, spraying or coating the epoxy resin layer with a layer of aggre-gates. When the ~hickness of the epoxy layer is suf-ficient to provide sufficient rigidity, the shell can be readily removed from the mould. On the other hand, when the epoxy layer is so thin that the shell cannot be removed from the mould, it is then preferable to pour the concrete in the shell unit and after curing of the concrete the whole unit is then removed from the shell thus providing a moulded concrete shape having at least one face coated and thus protected wi$h an epoxy resin.
Also, in a further aspect of the present invention, the layer of aggregate partially embedded in the cured epoxy resin layer can be sprayed with a thin layer of fiber reinforced concrete which will provide the required rigidity and after allowing the reinforced concrete to set, the moulded shsll is removed from the shaping mould and can then be transported to a building site so that concxete may be poured in the moulded shell, thus ~2~
avoiding the transportation of large moulded epoxy resin coated concrete units.
In a further aspect, the mould~ after the spraying or coating of the aggregate and after the epoxy resin is cured, can be filled at any time with cement concrete and, after allowing the unit to set/ the epoxy coated concrete unit is removed from the shaping mould giving a finished concrete unit having at least one face coated with an epoxy resin and the unit can then be transported ~o a building site for installation.
Furthermore, it has been found that the method of the present invention is sui~able for moulding shapes having a vertical, inclined, horizontal or curved surface, thus providing a moulded cement concrete unit of the desired shape and coated ox protected with an outer rigid epoxy resin shell.
DETAILED DESCRIPTION OF THE INVENTION
-In its broadest aspect, the moulded shell units of the present invention are prepared by a method 2Q which comprises applying a layer of epoxy resin to at least one inner surface of a shaping mould which is non~
bonding to epoxy resins, coating the uncured epoxy resin surface with a layer of aggregates and, after allowing the epoxy resin to cure, removing the moulded epoxy resin shell having aggregates embedded in its inner surface. The moulded shPll can then be used to prepare finished concrete products having part of the outside surfaces coated with epoxy resin by pouring concrete in the shell and allowing the concrete to cure whereby said cured concrete will be mechanically bonded with the aygregates which are partially embedded in the cured epoxy resin.
Where it is desired to mould larger unit, it is necessary to provide a moulded shell having suffi-cient rigidity for transportation to the site and suf--ficient resistance to be used as a mould. Accordingly, the method comprises the further step of spraying onto the inner aggregate layer of the moulded shell previ-ously obtained with a lay~r of fiber reinforced concrete which mechanically binds with the layer of aggregates and, after curing said fiber reinforced concrete layer~
the moulded shell unit, after removal from the shaping mould, has sufficient strength and rigidity to be trans-ported to a desired site where concrete will be poured into the unit.
THE MOULDING SURFACE
An important feature of the present invention is the selection of a moulding surface or a mould which is non-bonding to epoxy resins thus avoiding the use of a parting layer required to be applied to the moulding surface or mould in prior art procedures.
In accordance with -the present invention, the shaping mould is made from a material which is itself non-bonding to epoxy resins~ Thus, the shaping mould can be a moulded shape of polyethylene, polypropylene or Teflon and the like. If desired, patterns can be present in the original mould so that moulds which are non-bonding to epoxy resins will be obtained with corre~
sponding patterns or designs thus eventually providing epoxy resin shellshaving the corresponding patterns or designs on their outer surface.
It is also possible to use an ordinary mould, such as wood, and line same with a plastic sheet of a material which is non-bonding to epoxy resins such as polyethylene, polypropylene, Teflon or the like. In this case the plastic sheet can readily be peeled from the cured epoxy resin shell after its removal from the shaping mould.
It will now be appreciated that in previous procedures the moulding surface was coated with a parting or demoulding agent such as polyvinylacetate, waxes or oils to prevent adhesion of the resin layer to the mould surface. In practice this procedure usually led to a mould which could not be readily reused without prior preparation. Furthermore, the moulding surface required elaborate preparation to insure proper and even application of the parting layer to avoid bonding of the epoxy resin layer to the moulding surface r~sulting either in a damaged moulded unit or damaged moulding surface or both. Accordingly, all the undesirable features are eliminated by using the novel moulding surface o~ the present invention.
THE EPOXY RES I N
The epoxy resin is applied ayainst the mould surface which is non-binding to epoxy resin in any suitable manner, such as, by spray, coating with a trowel, a brush or the like.
The thickness of the epoxy resin layer in general can vary from 0.1 mm to 10 mm but in some cases a thick~r coating may be required such as in cases where the epoxy resin layer will b~ subjected to severe abrasive conditions such as road markers where the epoxy layer may be as much as 1 to 1.5 cm in thickness. In many cases, ~he thickness of the epoxy resin layer will be dictated by economical factors, appreciating the cost of epoxy resins, and the intended use of the moulded units~
As fax as the epoxy resin, there is a vast selection available extending from low viscosity to high viscosity. When using a high viscosity, usually one coat is sufficient while when usiny a low viscosity epoxy resin, it is preferable to allow the first coat to cure and then apply a second coat and in some cases, when needed a third coat of low viscosity or even of high viscosity epoxy resin.
Epoxy resins constitute a well defined class of binding resins and are characterized by the opening of epoxy groups in the polymerization process.
~2~
A general description of the preparation o these epoxy resins is presented in the Encyclopedia of Polymer Science and Technology, page 209-271, volume 6, Intersciences Publishers, NYC, 1967. Another reference is "Hand~ook of Epoxy Resins" by H. Lee and K. Neville, McGraw Hill Book Co., Inc., 1967.
The epoxy resins used in accordance with the present invention are prepared from saturated polyhydric alcohols and phenols which contain no carbon to carbon unsaturation other than that which is present in the aromatic ring.
By the epoxy equivalency, reference is made the average number of 1,2-epoxy groups o (C~I2-C ) contained in the average molecule of the ether.
A preferred group of epoxy ethers for use in the invention is prepared by reacting a dihydric phenol with epichlorhydrin in alkaline solution. There products are of resinous character and frequently are solid materials at normal temperature ~20-30C~. Any of the various dihydric phenols are used in preparing these glycidyl ethers, including mononuclear phenols like resorcinol, catechol, hydroquinone, etc., or polynuclear phenols like bis-~4-hydroxyphenol)-2,2-propane ~bis-phenol A), 4,4'-dihydroxy benzophenone, bis-(4-hydroxy-phenyl)-l,l-ethane, bis-(4-hydroxyphenyl)-1,1-iso-butane, bis-(4-hydroxyphenyl)-2,2-butane, bic-(hydroxy-
2-tertiary butyl phenyl)-2,2-propane, bis-(hydroxy-~-tertiary butyl phenyl)-2,2 propane, bis-(2-hydroxy-naphthyl~-methane, l,S-dihydroxy naphthalene~ etc. The product may be represented by the formula:
-CH2-CH-CH2-(0-R-O-CH2-CHOH-CH2)n-0-R-O-CH2-CH-CH-wherein n is an integer, e.g. from 1 to 7, and R repre-sents the divalent hydrocarbon radical of the dihydric phenol.
There can be used 1,2-epoxy-containing poly-ethers of polyhydric alcohols, such as polyglycidyl ethers thereof, like the diglycidyl ether of ethylene glycol, propylene glycol, trimethylene glycol, diethyl-ene glycol, triethylene glycol, glycerol, dipropylene glycol and the like. Other typical ethers of this class include glycidyl ethers of polyhydric alcohols having a 1,2-epoxy equivalency greater than one, such as the polyglycidyl ethers of glycol, diglycerol, erythritol, pentaglycerol, mannitol, sorbitol, and the like.
As an example of suitable epoxy resins, there may be mentioned BAKELITE ERL-2744 of Union Carbide Corp. for a liquid bisphenol A epoxy resin having an epoxide equivalent of 185-200, BAKELITE ERL-4221 of Union Carbide Corp. for a liquid cycloaliphatic epoxy resin havlng an epoxide equivalent of 131-143, EPON 1002 or of Shell Oil Co. for solid bisphenol A epoxy resins having an epoxide equivalent of 600-700, EPON 1004 of Shell Oil Co. for solid bisphenol A epoxy resin having an epoxide equivalent of 870-1025, EPON 828 of Shell Oil Co. which is a diglycidyl ether of bisphenol A, ARALDITE 6010 of Ciba-Geigy Corp. for a liquid bis-phenol A epoxy resin having an epoxide Pquivalent of 185-196 and a product manufactured and sold by Reichold under the trademark QT-1219. Thus there can be used, for example, bisphenol A-epichlorhydrin resins.
If desired, dyes can ~e incorporated in the epoxy r~sin so as to obtain a corresponding coloured epoxy resin shell. In some cases, it may be desirable to use a transparent epoxy resin with a coloured aggre-gate so that the finished epoxy shell will be spotted with the coloured aggregate.
The epoxy resin can be cured at room temper-ature or the curing time can be accelerated by supply-ing a small amount of heat.
The epoxy resin can be applied to the mould with a brush or sprayed and therefore one should select the viscosity of the epoxy resin accordinglyO :[f a high viscosity epoxy resin is used, it will be applied with a trowel, roller or the like.
The epoxy resin is applied with a diluent as is well known in the art. As an example of a suitable diluent there may be mentioned butyl glycidyl ether sold as EPOXIDE 8 by the Wilmington Chemical Corp.
In some instances, the epoxy resin may include an ultraviolet absorber or ultraviolet screen such as a mixture of a nickel complex and zinc oxide or a nickel complex thiobisphenol light stabiliz~r with an inert metallic oxide. A suitable ultraviolet absorber is the product sold by Ferro Industrials Products Ltd under the trademark UV CHECK AM 105.
To facilitate spraying or spreading of the epoxy resin a wetting agent such as glycerine is used.
There may also be used a thixotropic agent such as fumed silica, for example, a colloidal pyrogenic silica pigment scld as CAB-O-SIL by Cabot Corporation.
Inert charges such as pulverized silicium such as INSIL 1240 sold by Illinois Minerals can also be included along with powdered pigments such as titanium dioxide or liquid pigments for example carbon black paste such as EP-90 sold by Duochem Co.
There will also be advantageously added hardeners such as triethylene tetraamine or aliphatic polyamines. The product sold under the trademark DEH-24 by Dow Chemical is an example of a suitable hardener.
Also, accelerators such as any proton donor~
for example, acids, phenols and alcohols may advanta-geously be included. As a suitable proton donor theremay be mentioned the product sold by Texaco Chemical under the trademark AOC~399.
AGGREGATES
The aggregates used are those readily availa-ble on the market in various sizes and colors. As far as the aggregates are concerned, it is preferable to use those having angular ~dges, but even a certain amount of round aggregates can be used. I~he size of the aggre-gates may vary from 2 mm to 10 mm or more if desired.
The aggregates can be sprayed onto the uncured epoxy resin with an air gun or any other suitable mechanical means such as those readily available on the market, or also applied manually.
GLASS REINFORCED CONCRETE
In those cases where the desired end product is so large that it may be an advantage that the concrete be pou~ed into the cured epoxy resin shell on the site of its use, then it is pxeferable that suffi-cient rigidity be provided for its transportation.
Accordingly the aggregate layer of the epoxy resin shell is coated with a layer of glass reinforced concrete which, upon curing, will be mechanically bonded to the aggregates. ThR glass reinforced concrete layer is light enough and provides sufficient rigidity to the unit to allow its transportation to any site and for its easy use.
~ 15 -In general the thickness of the glass rein-forced concrete layer will vaxy from 1/4 to 3/4" which provides the desired flexibility and rigidity for the intended purposes. A much thicker layer of Portland cement concrete would have to be used to obtain the desired rigidity but with a loss in flexibility and a substantial increase in weight.
CONCRETE
As far as the concrete which can be poured into the epoxy resin shell units of the present in-vention, any of the commercially available c~ncrete can be used such as for example Portland cement concrete, refractory cement concrete or polymer concrete.
PROPERTIES OF EPOXY RESIN COATED CONCRETE UNITS
It has been found that epoxy resin coated concrete units, prepared in accordance with the present invention, are highly resistant to degradation when sub-jected to the A.S.T.M. B-1117-73 "Standard Method of Salt Spray (Fog~ Testing". Units prepared in accordance with the present invention were not altered after 3~661 hours of testing while units prepared with a polyester resin became powdery after 500 hours and showed cracking and separation of the resin after 800 hours.
~ hen submitted to a series of cycles of freeæing and thawing as prescribed by AoS~T~M~ C~666-77 "Resistance of Concrete to Rapid Freezing and Thawing, procedure A", it was obs;erved that no change occurred up to 846 cycles while units coated with a polyester resin started to disintegrate after 50 cycles.
EXAMPI.E I
SE~MI-CYLINDRICAL PANEL
A 1/4" board of polypropylene is used as a mould surface because it is non-bonding to epoxy resins.
This flexible board i5 placed in a wooden frame to provide a shape of the panel which is a semi-cylinder having a diameter of 4 feet and a length of 8 feet. The moulded panel to be prepared is to be used as a perma-nent form in the repair and restoration of concrete columns. The epoxy coated panel is prepared by the following steps.
The polypropylene surface is coated with a layer of about 1.5 mm in thickness of an uncured epoxy resin manufactured by Shell Chemical and sold under the trademark "EPON 828". The uncured epoxy resin layer is then coated with a layer of angular calcium aggregates having 3 to 5 mm in size which are partially embedded in the ~ncured layer of epoxy resin. The epoxy resin is then allowed to cure for three hours whereby there is obtained a moulded and cured epoxy resin shell having angular aggre~ates partially embedded therein. The layer of aggregates is then coated with a layer of fibre reinforced concrete to a thickness of 3/4 of an inch and after allowing the reinforced concrete to cure there is obtained a semi-cylindrical shell which can easily be ~ .
stripped from the wood moulding frame. Th~ shell has sufficient rigidity and strength to be transported to a site for use as a permanent form. The outer shell of the same ,cylindrical form and the inner layer of the fibre reinforced concrete are mechanically bonded together by means of the intermediate ],ayer of aggre-gates partially embedded in the cured epoxy resin layer and partially embedded in the cured glass fibre rein-forced concrete.
INSTALLATION ON JOB-SITE
_ Deteriorated concrete is removed from a concrete column and the exposed reinforcing steel is cleaned as is well known in the art. Then, two semi-cylindrical panels as prepared previously are placed around the concrete column to form the cylinder and the two panels are held together by means of binding metal straps while the vertical joints of the two panels are filled and sealed with asphalt rubber joint material well known in the art.
Fluid Portland cement concrete is poured into the shell and completely fills the space between the inner concrete column and the outer cylindrical shell.
After allowing the Portland cement concrete to cure and harden, the metal straps are removed, the epoxy resin cured cylindrical shell now constitutes an integral part of the concrete column and provides protection against deicing as well as freezing and thawing.
XAMPLE I I
EPOXY RES IN COATED CONCRETE STEPS
A board of polyethylene having a textured surface is used as a mould because it is non binding to epoxy resin. The textured surface of the mould will provide an anti-slip surface on the finished product.
The mould was 40 inches in length, 13 inches in width and had a flange on one side of 1 1/2ll.
The inner mould surface was coatPd with a layer of 1 mm of epoxy resin (EPON 828) and immediately after, th~ epoxy resin layer was coated with a layer of angular aygregates which w~re partially embedded in the uncured layer of epoxy resin. The epoxy resin was then allowed to cure for a period of three hours, thus obtaining a moulded and cured epoxy resin form having angular aggregates partially embedded therein.
Then, the cured epoxy resin shell thus obtain-ed was filled with Portland cement concrete and after allowing the concrete to cure, the whole unit was stripped from the mould. The outer layer of cured epoxy resin and the inner layer of cured Portland cement concrete were mechanically bonded together by means of the intermediate layer of aggregates, partially embedded in the cured epoxy resin and partially embedded in the cured concretP layer.
INST~LLATION OF THE STEP
_ Deteriorated concrete on the surface of existing concrete steps is removed and -the exposed surface is then thoroughly cleaned. A layer of an adhesive epoxy resin or other suitable bonding material is then applied on the surface of the cleaned concrete step. The epoxy resin coated concrete step is then placed on the uncured material and the bonding matexial is then allowed to harden. If necessary, the joints between the steps can then be filled with cement mortar or other suitable jointing material such as silicone rubber.
EXAMPLE I I I
EPOXY RESIN CONCRET~5 SI~BS
A polypropylene mould which is not bonding to epoxy resin in the form of an open box 12 inches by 1~
inches and 2 inches in height is used as a mould. The inside surface of the mould was textured to immitate slate.
The inside surface of the bottom face of the mould is coated with a layer of epoxy resin by spraying or manual coating to a thickness of l mm. The layer of uncured epoxy resin is then coated with a layer of angular aggreyates which are partially embedded in the uncured layer of epoxy resin. The epoxy resin is then permitted to cure and after curing the mould is Eilled with liquid Portland cement concrete and the outer surEace of the concrete is smoothed with a trowel.
After curing of the concrete, the epoxy resin concrete ffl~a unit or slab i5 stripped from the mould. Preferably before the pouring of the concrete, the plastic mould is inserted in a steel frame to prevent buckling of the sides of the plastic mould because of the weight of the fresh concrete.
The thus obtained epoxy resin coated concrete slab is suitable for use in making patios, driveways or walkways.
-CH2-CH-CH2-(0-R-O-CH2-CHOH-CH2)n-0-R-O-CH2-CH-CH-wherein n is an integer, e.g. from 1 to 7, and R repre-sents the divalent hydrocarbon radical of the dihydric phenol.
There can be used 1,2-epoxy-containing poly-ethers of polyhydric alcohols, such as polyglycidyl ethers thereof, like the diglycidyl ether of ethylene glycol, propylene glycol, trimethylene glycol, diethyl-ene glycol, triethylene glycol, glycerol, dipropylene glycol and the like. Other typical ethers of this class include glycidyl ethers of polyhydric alcohols having a 1,2-epoxy equivalency greater than one, such as the polyglycidyl ethers of glycol, diglycerol, erythritol, pentaglycerol, mannitol, sorbitol, and the like.
As an example of suitable epoxy resins, there may be mentioned BAKELITE ERL-2744 of Union Carbide Corp. for a liquid bisphenol A epoxy resin having an epoxide equivalent of 185-200, BAKELITE ERL-4221 of Union Carbide Corp. for a liquid cycloaliphatic epoxy resin havlng an epoxide equivalent of 131-143, EPON 1002 or of Shell Oil Co. for solid bisphenol A epoxy resins having an epoxide equivalent of 600-700, EPON 1004 of Shell Oil Co. for solid bisphenol A epoxy resin having an epoxide equivalent of 870-1025, EPON 828 of Shell Oil Co. which is a diglycidyl ether of bisphenol A, ARALDITE 6010 of Ciba-Geigy Corp. for a liquid bis-phenol A epoxy resin having an epoxide Pquivalent of 185-196 and a product manufactured and sold by Reichold under the trademark QT-1219. Thus there can be used, for example, bisphenol A-epichlorhydrin resins.
If desired, dyes can ~e incorporated in the epoxy r~sin so as to obtain a corresponding coloured epoxy resin shell. In some cases, it may be desirable to use a transparent epoxy resin with a coloured aggre-gate so that the finished epoxy shell will be spotted with the coloured aggregate.
The epoxy resin can be cured at room temper-ature or the curing time can be accelerated by supply-ing a small amount of heat.
The epoxy resin can be applied to the mould with a brush or sprayed and therefore one should select the viscosity of the epoxy resin accordinglyO :[f a high viscosity epoxy resin is used, it will be applied with a trowel, roller or the like.
The epoxy resin is applied with a diluent as is well known in the art. As an example of a suitable diluent there may be mentioned butyl glycidyl ether sold as EPOXIDE 8 by the Wilmington Chemical Corp.
In some instances, the epoxy resin may include an ultraviolet absorber or ultraviolet screen such as a mixture of a nickel complex and zinc oxide or a nickel complex thiobisphenol light stabiliz~r with an inert metallic oxide. A suitable ultraviolet absorber is the product sold by Ferro Industrials Products Ltd under the trademark UV CHECK AM 105.
To facilitate spraying or spreading of the epoxy resin a wetting agent such as glycerine is used.
There may also be used a thixotropic agent such as fumed silica, for example, a colloidal pyrogenic silica pigment scld as CAB-O-SIL by Cabot Corporation.
Inert charges such as pulverized silicium such as INSIL 1240 sold by Illinois Minerals can also be included along with powdered pigments such as titanium dioxide or liquid pigments for example carbon black paste such as EP-90 sold by Duochem Co.
There will also be advantageously added hardeners such as triethylene tetraamine or aliphatic polyamines. The product sold under the trademark DEH-24 by Dow Chemical is an example of a suitable hardener.
Also, accelerators such as any proton donor~
for example, acids, phenols and alcohols may advanta-geously be included. As a suitable proton donor theremay be mentioned the product sold by Texaco Chemical under the trademark AOC~399.
AGGREGATES
The aggregates used are those readily availa-ble on the market in various sizes and colors. As far as the aggregates are concerned, it is preferable to use those having angular ~dges, but even a certain amount of round aggregates can be used. I~he size of the aggre-gates may vary from 2 mm to 10 mm or more if desired.
The aggregates can be sprayed onto the uncured epoxy resin with an air gun or any other suitable mechanical means such as those readily available on the market, or also applied manually.
GLASS REINFORCED CONCRETE
In those cases where the desired end product is so large that it may be an advantage that the concrete be pou~ed into the cured epoxy resin shell on the site of its use, then it is pxeferable that suffi-cient rigidity be provided for its transportation.
Accordingly the aggregate layer of the epoxy resin shell is coated with a layer of glass reinforced concrete which, upon curing, will be mechanically bonded to the aggregates. ThR glass reinforced concrete layer is light enough and provides sufficient rigidity to the unit to allow its transportation to any site and for its easy use.
~ 15 -In general the thickness of the glass rein-forced concrete layer will vaxy from 1/4 to 3/4" which provides the desired flexibility and rigidity for the intended purposes. A much thicker layer of Portland cement concrete would have to be used to obtain the desired rigidity but with a loss in flexibility and a substantial increase in weight.
CONCRETE
As far as the concrete which can be poured into the epoxy resin shell units of the present in-vention, any of the commercially available c~ncrete can be used such as for example Portland cement concrete, refractory cement concrete or polymer concrete.
PROPERTIES OF EPOXY RESIN COATED CONCRETE UNITS
It has been found that epoxy resin coated concrete units, prepared in accordance with the present invention, are highly resistant to degradation when sub-jected to the A.S.T.M. B-1117-73 "Standard Method of Salt Spray (Fog~ Testing". Units prepared in accordance with the present invention were not altered after 3~661 hours of testing while units prepared with a polyester resin became powdery after 500 hours and showed cracking and separation of the resin after 800 hours.
~ hen submitted to a series of cycles of freeæing and thawing as prescribed by AoS~T~M~ C~666-77 "Resistance of Concrete to Rapid Freezing and Thawing, procedure A", it was obs;erved that no change occurred up to 846 cycles while units coated with a polyester resin started to disintegrate after 50 cycles.
EXAMPI.E I
SE~MI-CYLINDRICAL PANEL
A 1/4" board of polypropylene is used as a mould surface because it is non-bonding to epoxy resins.
This flexible board i5 placed in a wooden frame to provide a shape of the panel which is a semi-cylinder having a diameter of 4 feet and a length of 8 feet. The moulded panel to be prepared is to be used as a perma-nent form in the repair and restoration of concrete columns. The epoxy coated panel is prepared by the following steps.
The polypropylene surface is coated with a layer of about 1.5 mm in thickness of an uncured epoxy resin manufactured by Shell Chemical and sold under the trademark "EPON 828". The uncured epoxy resin layer is then coated with a layer of angular calcium aggregates having 3 to 5 mm in size which are partially embedded in the ~ncured layer of epoxy resin. The epoxy resin is then allowed to cure for three hours whereby there is obtained a moulded and cured epoxy resin shell having angular aggre~ates partially embedded therein. The layer of aggregates is then coated with a layer of fibre reinforced concrete to a thickness of 3/4 of an inch and after allowing the reinforced concrete to cure there is obtained a semi-cylindrical shell which can easily be ~ .
stripped from the wood moulding frame. Th~ shell has sufficient rigidity and strength to be transported to a site for use as a permanent form. The outer shell of the same ,cylindrical form and the inner layer of the fibre reinforced concrete are mechanically bonded together by means of the intermediate ],ayer of aggre-gates partially embedded in the cured epoxy resin layer and partially embedded in the cured glass fibre rein-forced concrete.
INSTALLATION ON JOB-SITE
_ Deteriorated concrete is removed from a concrete column and the exposed reinforcing steel is cleaned as is well known in the art. Then, two semi-cylindrical panels as prepared previously are placed around the concrete column to form the cylinder and the two panels are held together by means of binding metal straps while the vertical joints of the two panels are filled and sealed with asphalt rubber joint material well known in the art.
Fluid Portland cement concrete is poured into the shell and completely fills the space between the inner concrete column and the outer cylindrical shell.
After allowing the Portland cement concrete to cure and harden, the metal straps are removed, the epoxy resin cured cylindrical shell now constitutes an integral part of the concrete column and provides protection against deicing as well as freezing and thawing.
XAMPLE I I
EPOXY RES IN COATED CONCRETE STEPS
A board of polyethylene having a textured surface is used as a mould because it is non binding to epoxy resin. The textured surface of the mould will provide an anti-slip surface on the finished product.
The mould was 40 inches in length, 13 inches in width and had a flange on one side of 1 1/2ll.
The inner mould surface was coatPd with a layer of 1 mm of epoxy resin (EPON 828) and immediately after, th~ epoxy resin layer was coated with a layer of angular aygregates which w~re partially embedded in the uncured layer of epoxy resin. The epoxy resin was then allowed to cure for a period of three hours, thus obtaining a moulded and cured epoxy resin form having angular aggregates partially embedded therein.
Then, the cured epoxy resin shell thus obtain-ed was filled with Portland cement concrete and after allowing the concrete to cure, the whole unit was stripped from the mould. The outer layer of cured epoxy resin and the inner layer of cured Portland cement concrete were mechanically bonded together by means of the intermediate layer of aggregates, partially embedded in the cured epoxy resin and partially embedded in the cured concretP layer.
INST~LLATION OF THE STEP
_ Deteriorated concrete on the surface of existing concrete steps is removed and -the exposed surface is then thoroughly cleaned. A layer of an adhesive epoxy resin or other suitable bonding material is then applied on the surface of the cleaned concrete step. The epoxy resin coated concrete step is then placed on the uncured material and the bonding matexial is then allowed to harden. If necessary, the joints between the steps can then be filled with cement mortar or other suitable jointing material such as silicone rubber.
EXAMPLE I I I
EPOXY RESIN CONCRET~5 SI~BS
A polypropylene mould which is not bonding to epoxy resin in the form of an open box 12 inches by 1~
inches and 2 inches in height is used as a mould. The inside surface of the mould was textured to immitate slate.
The inside surface of the bottom face of the mould is coated with a layer of epoxy resin by spraying or manual coating to a thickness of l mm. The layer of uncured epoxy resin is then coated with a layer of angular aggreyates which are partially embedded in the uncured layer of epoxy resin. The epoxy resin is then permitted to cure and after curing the mould is Eilled with liquid Portland cement concrete and the outer surEace of the concrete is smoothed with a trowel.
After curing of the concrete, the epoxy resin concrete ffl~a unit or slab i5 stripped from the mould. Preferably before the pouring of the concrete, the plastic mould is inserted in a steel frame to prevent buckling of the sides of the plastic mould because of the weight of the fresh concrete.
The thus obtained epoxy resin coated concrete slab is suitable for use in making patios, driveways or walkways.
Claims (3)
1. A moulded shell for forming or repairing concrete structural units comprising: an outer layer of cured epoxy resin, said layer having an inner and outer surface, an intermediate layer of aggregates partially embedded in said inner surface, and an inner layer of cured fiber reinforced concrete mechanically bonded to the intermediate layer of aggregates to define an adhering surface to concrete whereby said shell remains adhered to a concrete structural unit when formed or repaired.
2. A method for preparing a moulded unit shell which comprises:
a) coating a mould surface which is non-bonding to epoxy resins with a layer of epoxy resin, b) coating the uncured exposed face of the epoxy resin layer with a layer of angular aggregates, c) coating the layer of partially embedded angular aggregates with a layer of fiber reinforced con-crete, and d) after curing of said fiber reinforced concrete, removing the moulded unit shell from the mould.
a) coating a mould surface which is non-bonding to epoxy resins with a layer of epoxy resin, b) coating the uncured exposed face of the epoxy resin layer with a layer of angular aggregates, c) coating the layer of partially embedded angular aggregates with a layer of fiber reinforced con-crete, and d) after curing of said fiber reinforced concrete, removing the moulded unit shell from the mould.
3. A method according to Claim 2 further comprising pouring a cement concrete on the layer of partially embedded angular aggregates, allowing the cement concrete to cure whereby there is obtained a moulded concrete unit coated with a rigid epoxy resin layer, and removing the moulded unit thus obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000416219A CA1214914A (en) | 1982-11-24 | 1982-11-24 | Structural units and method for forming same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000416219A CA1214914A (en) | 1982-11-24 | 1982-11-24 | Structural units and method for forming same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1214914A true CA1214914A (en) | 1986-12-09 |
Family
ID=4124010
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000416219A Expired CA1214914A (en) | 1982-11-24 | 1982-11-24 | Structural units and method for forming same |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1214914A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0327957A2 (en) * | 1988-02-07 | 1989-08-16 | Mohamed Kamal Dr. Ing. El Sayed Moustafa | A method for manufacturing marble-like products with combined cross section of synthetic resin and cement or gypsum based layers |
| FR2692305A1 (en) * | 1992-06-16 | 1993-12-17 | Altor Sa | Moulded, prefabricated, ready-to-use sanitary unit - has internal polyester, phenolic, epoxy] or silicone moulding joined by loops in fibre glass reinforcement to core of concrete lightened with polyester balls, wood chip or vermiculite |
| WO1998016721A1 (en) * | 1996-10-15 | 1998-04-23 | C. I. Kasei Co., Ltd. | Resin-coated segment, and manufacture thereof |
-
1982
- 1982-11-24 CA CA000416219A patent/CA1214914A/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0327957A2 (en) * | 1988-02-07 | 1989-08-16 | Mohamed Kamal Dr. Ing. El Sayed Moustafa | A method for manufacturing marble-like products with combined cross section of synthetic resin and cement or gypsum based layers |
| EP0327957A3 (en) * | 1988-02-07 | 1990-07-25 | Mohamed Kamal Dr. Ing. El Sayed Moustafa | A method for manufacturing marble-like products with combined cross section of synthetic resin and cement or gypsum based layers |
| FR2692305A1 (en) * | 1992-06-16 | 1993-12-17 | Altor Sa | Moulded, prefabricated, ready-to-use sanitary unit - has internal polyester, phenolic, epoxy] or silicone moulding joined by loops in fibre glass reinforcement to core of concrete lightened with polyester balls, wood chip or vermiculite |
| WO1998016721A1 (en) * | 1996-10-15 | 1998-04-23 | C. I. Kasei Co., Ltd. | Resin-coated segment, and manufacture thereof |
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