CA1094111A - Composition and method for producing glass reinforced cement products - Google Patents
Composition and method for producing glass reinforced cement productsInfo
- Publication number
- CA1094111A CA1094111A CA300,778A CA300778A CA1094111A CA 1094111 A CA1094111 A CA 1094111A CA 300778 A CA300778 A CA 300778A CA 1094111 A CA1094111 A CA 1094111A
- Authority
- CA
- Canada
- Prior art keywords
- glass
- cement
- glass reinforcement
- water soluble
- reinforcement fibers
- 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
-
- 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
- C04B28/02—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 hydraulic cements other than calcium sulfates
-
- 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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
-
- 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/04—Carboxylic acids; Salts, anhydrides or esters thereof
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0004—Compounds chosen for the nature of their cations
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0004—Compounds chosen for the nature of their cations
- C04B2103/0021—Compounds of elements having a valency of 3
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00482—Coating or impregnation materials
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
COMPOSITION AND METHOD FOR PRODUCING
GLASS REINFORCED CEMENT PRODUCTS
Abstract of the Disclosure A cement mix suitable for mixing with water to form a glass reinforced cementitious material for use in high tensile strength applications such as surface bonding of concrete blocks or the like or in the for-mation of concrete products and characterized by a resistance to degradation of the glass reinforcement by the alkaline environment of the cementitious material. The cement mix comprises a dry mixture of an inorganic cementitious binder containing at least one reactive alkali compound, glass rein-forcement fibers, and a water soluble salt of a metal selected from the group con-sisting of barium, lithium, and zinc.
GLASS REINFORCED CEMENT PRODUCTS
Abstract of the Disclosure A cement mix suitable for mixing with water to form a glass reinforced cementitious material for use in high tensile strength applications such as surface bonding of concrete blocks or the like or in the for-mation of concrete products and characterized by a resistance to degradation of the glass reinforcement by the alkaline environment of the cementitious material. The cement mix comprises a dry mixture of an inorganic cementitious binder containing at least one reactive alkali compound, glass rein-forcement fibers, and a water soluble salt of a metal selected from the group con-sisting of barium, lithium, and zinc.
Description
COMPOSITION AND METHOD FOR PRODUCING
GLASS REINFORCED CEMENT PRODUCTS
This invention rel~tes to the utilization of glass as a reinforcement for cementitious articles, and more partic-ularly to a method and composition whereby attack and degradation of the ~lass reinforcement by the alkali content of the inorganic cementitious binder is eliminated or greatly reduced.
Back~round of the Inventlon The use o~ glass as a reinforcement for cementitious materials such as concrete has been investigated for many yearsO Consideration has been given to the use of glass fiber rods to replace conventional steel reinforcement, as well as to the use of glass reinforcement in the form of fibers, flakes and woven or non-woven fabrics. Particular attention has been given recently to the use of glass fibers as a reinforcement for concrete and cement.
A serious obstacle in employing glass as a reinforce-ment in cement and concrete is the alkaline environment of the inorganic cementitious binder, which is highly deleterious to the glass and results in significant loss of strength in the reinforced cement or concrete products over a period of time, or even in total destruction of the glass reinforcement.
Attack and destruction of the glass reinforcing properties is particularly rapid under humid conditions.
Prior approaches to overcoming the problem of alkali attack of the glass reinforcement have included the use of low alkali t~pe cements, the use of coatings to protect the glass from the alkali, the use of specialized alkali resistant glass compositions, and the use of a ca~ion exchange material to change the inorganic alkaline binder into a form which does not attack the glass~ ~he most active areas of investi-gation appear to be the use of protective coatings for the ~i 'Y'Y~
4~
glass and the dPvelopmcllt of alkali resis~ant glass compositionas evidenced, ~or ex.-mple by several very recent patents, e.g., U.S. patents 4,002,48~ and 4~Q13~s78.
However, the above-mentioned prior approach~s have not been entirely successful in prodl.~cing a practical, commercial glass reinforced cement compositioIl. The limited availability and expense of the speciali~ed materials required in these approaches renders the use of these materials unfeasible for many applications. `
Summary of the Invention The present invention departs entirely from the above-noted traditional areas of investigati.on and research in protecting glass reinforcernent fibexs. Moreover, in accordance with the present invention it has heen determined that certain water soluble salts r when incorporated in a cement composition containing glass reinforcing fibers, may be used most effectively to inhibit alkali attack upon the glass reinforcement fibers in the cement composition.
More particularly, in accordance with this invention it has been determined that water soluble salts of a metal selected from the group consisting of barium, lithium, a.nd zinc, when mixed in finely divided particulate form with the dry cementitious binder and glass reinforcement, are highly ef~ective to inhibit alkali degradati.on of the glass reinforce-ment when the cement mix is mixed with water and allowed tocure to form a cured glass reinforced cement product.
Thus, the method is directed to a method of making glass reinforced cementitious material comprising the steps of adding water to a mi~ture of inoryanic alkaline cementitious binder and glass reinforcemen~ ~-bers, mixiny the components and allowing the mixture to harden and cure; characterized by inhibiting de~radation of the glass reinforcement fibers -~ -2~
- .
in the alkaline envi.ronment of the cementitious binder by adding to the ml~ture of inorganic cementitious binder and glass reinforcement fibers, from one-half to fifty percent by weight based upon the weight of the glass reinforcement 5 fi.bers of finely divided parti.cles of a water soluble salt of a metal selected from the group consisting of barium, lithi~m and zinc.
The present invention is further directed to a method of making a surface bonded wall comprising the steps of applying a coatiny of a surface bonding cement over at least one surface of an assembly of stacked concrete blocks and allowing the cement coating to harden and cure and serve to bond the blocks together without the necessity ofmortar between the blocks, and wherein said coating of surface bonding cement comprises an inorganic cementitious binder containing at ieast one reactive alkali compound, glass reinforcement fibers distributed throughout the binder, and fine sand aggregate also distributed throughout the binder; characterized by inhibiting degradation of the glass reinforcement fibers in the alkaline environment 20 of the cementitious binder by adding to the mixture of inorganic cementitious binder, glass reinforcement fibers, and fine sand aggregate, from one-half to fifty percent by weight based upon the weight of the glass reinforcement fibers of finely divided particles of a water soluble salt of a metal selected from the group consisting of barium, lithium and zinc.
The present invention is also directed to a cement mix suitable for use in carrying out the above me~hodsa It .is known that water soluble salts of certain metals, such as bari.um and lithium for example, may be used in cement 2a-`) .
compositions as an inhibitor against undesixable and destructive expansion reactions between the alkali content of the cement binder and agyregateO
In accordance with the present invention it has been determined that certain of these water soluble metal salts, which were heretofore known to be e~fective to inhibit al~ali aggregate expansion reactions in cement, may be used quite effectively in a glass rein~orced cement composition ko protect the glass rein~orcement from the harmful alkaline environment of the cementitious binder.
The use of these water soluble metal salts in glass reinforced cement compositions in accor~ance with this invention permits the use of ordinary relatively inexpensive E-glass reinforcing fibers instead of the more expensive and sometimes unavailable alkali-resistant types of glass. It will be appreciated however, tha~ the metal salts may also be beneficially used i~ cement compositions containing alkali resistant glass reinforcing fibers and will provide an enhanced degree of alkali resistance thereto.
The glass reinforced cement mix compositions in accor-dance with this invention are suita~le for numerous applications, including use in high strength construction elements, cast or extruded concrete articles, and for surface bonding of concrete blocks or the like without the necessity of mortar between the blocks.
The inorganic binders used in accordance with the present invention may include Portland cement, masonry cement, mixtures of Portland c~ement and rnasonry cement, and mixtures of the foregoing with hydrated lime. The cement composition may also include aggregate fillers such as sand, and property-modifying additives such as piyments~ plasticizers, water reduciny admixtures, ~aterproo~ing admixtures, shrin~age ;
~ 6~
; compensators, set accelerators, retarders, gas forming agents, air entraining admixtures, and water retaining admixturesO
Some of the features and advantages of the invention having been stated, others will become apparent from the description and examples which follow, which are lntended to illustrate and disclose, but in no way limit, the invention.
Detailed Description of the Invention The chemicals found effective to inhibit alkali attack upon the glass reinforcement in a glass fiber reinforced cement product are water soluble salts of a metal selected ; rom the group consisting of barium, lithium, and zinc, and preferably the water soluble chloride, carbonate, nitrate, or acetate salt of such metalu Particularly preferred are barium chloride, zinc acetate, and lithium carbonate. The salt is incorporated into the cement mix by uniformly blending finely divided particles of the salt with the dry particulate cementitious bindex and glass reinforcement.
Cement mixes for forming glass reinforced cement products are conventionally sold pre-packaged in bags.
The water soluble salts found effective as inhibitors in accordance with this invention may be suitably mixed with the dry cementitious binder and ~lass reinforcement, packaged, stored for indefinite periods of time without loss of effectiveness as an inhibitor and without causing caking or lumping of the cement mix. The metal salt becomes active as an inhibitor when the cement mix is mixed with water and the composition is allowed to cure to form a cured cement product.
While the mechanism by which the water soluble metal salts function to inhibit alkali degradation of the glass reinforcement is not entirely understoGd, tests have determined that the metallic element becomes chemically attached .. ,~ . :
-or bonded to the glass in some manner, and that tha glass is protected from alkali attack thereby~ I t is believed that the metal reacts with the alkali reactive silica of the glass to produce a metal~silica complex which forms an alkali resistant protective sheath or coating on all exposes surfaces of the glass and thus insulates the glass from further reaction with the alkali content of the cement binder. It will be appreciated that since the reaction between the water soluble metal salt and the glass reinforcement occurs ln situ while the glass reinforcement is distributed in the alkaline cementitious binder matrix, all alkali susceptible sur~aces of the glass rein~orcement are protected b~ the inhibitor.
On the other hand, where a protective material is applied as a coating to glass reinforcement fibers as is done in accordance with many o~ the priox approaches as noted earlier, complete coverage of the glass fiber with the protective material cannot be achieved, since the protective material is normally applied to the continuous glass filaments prior ko cutting into fibers and the end surfaces of the fibers are thus left unprotected.
In the cured glass reinforced cement product of this invention, the metal is present not only on the surface of the glass rein~orcement fibers but also throughout the cement matrix, as a result of the water soluble metal salt having been blended with the alkaline cementitious binder prior to mixing of the cement and curingO The metal is thus a~ailable in the cement to provide additional protection to the glass reinforce-ment throughout the life o~ the glass reinforced cement productO
In this regard, it has been determined that under normal environmental conditions, the greatest amount of alkali degradation o~ the glass reinforcement occurs shortl~
after the cement is mlxedO After several months of curing, ~9~
the alkali remaining in the cement is relatively insoluble and non-aggressive, much of it having been neutralized by reaction with carbon dioxide in the atmosphere or with other materials in the cement.
However, where the cement product is used under severe conditions of high humidity and~or high temperature, the alkali may remain relatively active and aggressive ~or extended periods o~ time. Similarly, if the cement product is late~ exposed to these conditions, the relatively non-aggressive alkali may become reactivated. The metal which isdistributed throughout the cement matrix in accordance with this invention is available to provide additional protection to the glass rein~orcement, if and when the severe conditions occur.
The water soluble metal salts have been found to be effective in concentrations as low as about one-hal~
percent by weight based upon the weight of the glass reinforce-ment. Concentrations as high as about fifty percent by weight may be suitably employedr although the rate of increase in efectiveness as a function of concentration appears to level out somewhat at concentrations exceeding about ten to fifteen percent, and for this reason, concentrations significantly exceeding this level are not economically attractive. The salt is most desirably used in amounts ran~ing ~rom about one to about ten percent by weight based upon the weight o~ the ~lass reinforcement.
The alkaline inorganic binder employed in cement compositions in accordance with this invention may include masonry cement, Portland cemenk, mixtures of masonry cement and Portland cement, and mixtures of the above with hydrated lime. Portland cement is preferred and cements having an alkalinity as high as 1.5 percent by weight, based upon Na2O, may be suitably employed in the compositions of this invention.
6~
~-, Poxtland cements classified under ASTM specification C-150 as Type I cements have been tested and found particularly acceptable for the glass reinforced cement composi~ions of this invention.
The cement mix may also include the conventional types of fillers used in cement and concrete products such as gravel, sand, natural or manufactured aggregates, or crushed marble. Fine mineral aggregates (20 mesh or finer) `
are preferred in the compositions when chopped glass rein-forcement fibers are used to obtain proper dispersion of the glass reinforcement fibers and optimum reinforcing function thererom. The filler may be used in amounts ranging from 0 to 300 parts per 100 parts of dry cement binder.
Property modifying additives known in the cement and concrete industry as "admixtures" may also be included in the cement compositions. These are compounds or materials known to improve or alter the cement characteristics, and when used are generally incorporated in amounts of from about one percent up to about 20 percent by weight based upon the dry weight of the cement binder. Products classified as admixtures include pigments, water reducing admixtures, water retaining admixtures, air entraining ad~ixtures, set accelerators, gas forming additives, waterproofing admixtures, expansion producing admixtures, shrinkage compensation admixtures, and plasticizers.
The glass reinforcement may be in the form of fibersf chopped yarns or rovings, flakes, rods, and woven or non-woven fabrics. Preferably however, the reinforcement is in the form of individual glass fibers or bundles of fibers chopped to a length of about one-fourth inch to 2 inches, most desirably abo~-t one-half inch. Fibers shorter than about .
.: ' one-fourth inch are considerably less effective as reinforce-ment, while fibers in excess of about 2 inches become entangled or fo~n balls during mixing or o~herwise do not maintain adequate dispersion throughout the cement matrix. Commer-cially available borosilicate Type E-glass may be suitably employed. However, other types of co~nercially available glass, such as the various alkali resistant types of glass may also be employed if desired. The amoùnt of glass reinforcement employed is preferably within the range of
GLASS REINFORCED CEMENT PRODUCTS
This invention rel~tes to the utilization of glass as a reinforcement for cementitious articles, and more partic-ularly to a method and composition whereby attack and degradation of the ~lass reinforcement by the alkali content of the inorganic cementitious binder is eliminated or greatly reduced.
Back~round of the Inventlon The use o~ glass as a reinforcement for cementitious materials such as concrete has been investigated for many yearsO Consideration has been given to the use of glass fiber rods to replace conventional steel reinforcement, as well as to the use of glass reinforcement in the form of fibers, flakes and woven or non-woven fabrics. Particular attention has been given recently to the use of glass fibers as a reinforcement for concrete and cement.
A serious obstacle in employing glass as a reinforce-ment in cement and concrete is the alkaline environment of the inorganic cementitious binder, which is highly deleterious to the glass and results in significant loss of strength in the reinforced cement or concrete products over a period of time, or even in total destruction of the glass reinforcement.
Attack and destruction of the glass reinforcing properties is particularly rapid under humid conditions.
Prior approaches to overcoming the problem of alkali attack of the glass reinforcement have included the use of low alkali t~pe cements, the use of coatings to protect the glass from the alkali, the use of specialized alkali resistant glass compositions, and the use of a ca~ion exchange material to change the inorganic alkaline binder into a form which does not attack the glass~ ~he most active areas of investi-gation appear to be the use of protective coatings for the ~i 'Y'Y~
4~
glass and the dPvelopmcllt of alkali resis~ant glass compositionas evidenced, ~or ex.-mple by several very recent patents, e.g., U.S. patents 4,002,48~ and 4~Q13~s78.
However, the above-mentioned prior approach~s have not been entirely successful in prodl.~cing a practical, commercial glass reinforced cement compositioIl. The limited availability and expense of the speciali~ed materials required in these approaches renders the use of these materials unfeasible for many applications. `
Summary of the Invention The present invention departs entirely from the above-noted traditional areas of investigati.on and research in protecting glass reinforcernent fibexs. Moreover, in accordance with the present invention it has heen determined that certain water soluble salts r when incorporated in a cement composition containing glass reinforcing fibers, may be used most effectively to inhibit alkali attack upon the glass reinforcement fibers in the cement composition.
More particularly, in accordance with this invention it has been determined that water soluble salts of a metal selected from the group consisting of barium, lithium, a.nd zinc, when mixed in finely divided particulate form with the dry cementitious binder and glass reinforcement, are highly ef~ective to inhibit alkali degradati.on of the glass reinforce-ment when the cement mix is mixed with water and allowed tocure to form a cured glass reinforced cement product.
Thus, the method is directed to a method of making glass reinforced cementitious material comprising the steps of adding water to a mi~ture of inoryanic alkaline cementitious binder and glass reinforcemen~ ~-bers, mixiny the components and allowing the mixture to harden and cure; characterized by inhibiting de~radation of the glass reinforcement fibers -~ -2~
- .
in the alkaline envi.ronment of the cementitious binder by adding to the ml~ture of inorganic cementitious binder and glass reinforcement fibers, from one-half to fifty percent by weight based upon the weight of the glass reinforcement 5 fi.bers of finely divided parti.cles of a water soluble salt of a metal selected from the group consisting of barium, lithi~m and zinc.
The present invention is further directed to a method of making a surface bonded wall comprising the steps of applying a coatiny of a surface bonding cement over at least one surface of an assembly of stacked concrete blocks and allowing the cement coating to harden and cure and serve to bond the blocks together without the necessity ofmortar between the blocks, and wherein said coating of surface bonding cement comprises an inorganic cementitious binder containing at ieast one reactive alkali compound, glass reinforcement fibers distributed throughout the binder, and fine sand aggregate also distributed throughout the binder; characterized by inhibiting degradation of the glass reinforcement fibers in the alkaline environment 20 of the cementitious binder by adding to the mixture of inorganic cementitious binder, glass reinforcement fibers, and fine sand aggregate, from one-half to fifty percent by weight based upon the weight of the glass reinforcement fibers of finely divided particles of a water soluble salt of a metal selected from the group consisting of barium, lithium and zinc.
The present invention is also directed to a cement mix suitable for use in carrying out the above me~hodsa It .is known that water soluble salts of certain metals, such as bari.um and lithium for example, may be used in cement 2a-`) .
compositions as an inhibitor against undesixable and destructive expansion reactions between the alkali content of the cement binder and agyregateO
In accordance with the present invention it has been determined that certain of these water soluble metal salts, which were heretofore known to be e~fective to inhibit al~ali aggregate expansion reactions in cement, may be used quite effectively in a glass rein~orced cement composition ko protect the glass rein~orcement from the harmful alkaline environment of the cementitious binder.
The use of these water soluble metal salts in glass reinforced cement compositions in accor~ance with this invention permits the use of ordinary relatively inexpensive E-glass reinforcing fibers instead of the more expensive and sometimes unavailable alkali-resistant types of glass. It will be appreciated however, tha~ the metal salts may also be beneficially used i~ cement compositions containing alkali resistant glass reinforcing fibers and will provide an enhanced degree of alkali resistance thereto.
The glass reinforced cement mix compositions in accor-dance with this invention are suita~le for numerous applications, including use in high strength construction elements, cast or extruded concrete articles, and for surface bonding of concrete blocks or the like without the necessity of mortar between the blocks.
The inorganic binders used in accordance with the present invention may include Portland cement, masonry cement, mixtures of Portland c~ement and rnasonry cement, and mixtures of the foregoing with hydrated lime. The cement composition may also include aggregate fillers such as sand, and property-modifying additives such as piyments~ plasticizers, water reduciny admixtures, ~aterproo~ing admixtures, shrin~age ;
~ 6~
; compensators, set accelerators, retarders, gas forming agents, air entraining admixtures, and water retaining admixturesO
Some of the features and advantages of the invention having been stated, others will become apparent from the description and examples which follow, which are lntended to illustrate and disclose, but in no way limit, the invention.
Detailed Description of the Invention The chemicals found effective to inhibit alkali attack upon the glass reinforcement in a glass fiber reinforced cement product are water soluble salts of a metal selected ; rom the group consisting of barium, lithium, and zinc, and preferably the water soluble chloride, carbonate, nitrate, or acetate salt of such metalu Particularly preferred are barium chloride, zinc acetate, and lithium carbonate. The salt is incorporated into the cement mix by uniformly blending finely divided particles of the salt with the dry particulate cementitious bindex and glass reinforcement.
Cement mixes for forming glass reinforced cement products are conventionally sold pre-packaged in bags.
The water soluble salts found effective as inhibitors in accordance with this invention may be suitably mixed with the dry cementitious binder and ~lass reinforcement, packaged, stored for indefinite periods of time without loss of effectiveness as an inhibitor and without causing caking or lumping of the cement mix. The metal salt becomes active as an inhibitor when the cement mix is mixed with water and the composition is allowed to cure to form a cured cement product.
While the mechanism by which the water soluble metal salts function to inhibit alkali degradation of the glass reinforcement is not entirely understoGd, tests have determined that the metallic element becomes chemically attached .. ,~ . :
-or bonded to the glass in some manner, and that tha glass is protected from alkali attack thereby~ I t is believed that the metal reacts with the alkali reactive silica of the glass to produce a metal~silica complex which forms an alkali resistant protective sheath or coating on all exposes surfaces of the glass and thus insulates the glass from further reaction with the alkali content of the cement binder. It will be appreciated that since the reaction between the water soluble metal salt and the glass reinforcement occurs ln situ while the glass reinforcement is distributed in the alkaline cementitious binder matrix, all alkali susceptible sur~aces of the glass rein~orcement are protected b~ the inhibitor.
On the other hand, where a protective material is applied as a coating to glass reinforcement fibers as is done in accordance with many o~ the priox approaches as noted earlier, complete coverage of the glass fiber with the protective material cannot be achieved, since the protective material is normally applied to the continuous glass filaments prior ko cutting into fibers and the end surfaces of the fibers are thus left unprotected.
In the cured glass reinforced cement product of this invention, the metal is present not only on the surface of the glass rein~orcement fibers but also throughout the cement matrix, as a result of the water soluble metal salt having been blended with the alkaline cementitious binder prior to mixing of the cement and curingO The metal is thus a~ailable in the cement to provide additional protection to the glass reinforce-ment throughout the life o~ the glass reinforced cement productO
In this regard, it has been determined that under normal environmental conditions, the greatest amount of alkali degradation o~ the glass reinforcement occurs shortl~
after the cement is mlxedO After several months of curing, ~9~
the alkali remaining in the cement is relatively insoluble and non-aggressive, much of it having been neutralized by reaction with carbon dioxide in the atmosphere or with other materials in the cement.
However, where the cement product is used under severe conditions of high humidity and~or high temperature, the alkali may remain relatively active and aggressive ~or extended periods o~ time. Similarly, if the cement product is late~ exposed to these conditions, the relatively non-aggressive alkali may become reactivated. The metal which isdistributed throughout the cement matrix in accordance with this invention is available to provide additional protection to the glass rein~orcement, if and when the severe conditions occur.
The water soluble metal salts have been found to be effective in concentrations as low as about one-hal~
percent by weight based upon the weight of the glass reinforce-ment. Concentrations as high as about fifty percent by weight may be suitably employedr although the rate of increase in efectiveness as a function of concentration appears to level out somewhat at concentrations exceeding about ten to fifteen percent, and for this reason, concentrations significantly exceeding this level are not economically attractive. The salt is most desirably used in amounts ran~ing ~rom about one to about ten percent by weight based upon the weight o~ the ~lass reinforcement.
The alkaline inorganic binder employed in cement compositions in accordance with this invention may include masonry cement, Portland cemenk, mixtures of masonry cement and Portland cement, and mixtures of the above with hydrated lime. Portland cement is preferred and cements having an alkalinity as high as 1.5 percent by weight, based upon Na2O, may be suitably employed in the compositions of this invention.
6~
~-, Poxtland cements classified under ASTM specification C-150 as Type I cements have been tested and found particularly acceptable for the glass reinforced cement composi~ions of this invention.
The cement mix may also include the conventional types of fillers used in cement and concrete products such as gravel, sand, natural or manufactured aggregates, or crushed marble. Fine mineral aggregates (20 mesh or finer) `
are preferred in the compositions when chopped glass rein-forcement fibers are used to obtain proper dispersion of the glass reinforcement fibers and optimum reinforcing function thererom. The filler may be used in amounts ranging from 0 to 300 parts per 100 parts of dry cement binder.
Property modifying additives known in the cement and concrete industry as "admixtures" may also be included in the cement compositions. These are compounds or materials known to improve or alter the cement characteristics, and when used are generally incorporated in amounts of from about one percent up to about 20 percent by weight based upon the dry weight of the cement binder. Products classified as admixtures include pigments, water reducing admixtures, water retaining admixtures, air entraining ad~ixtures, set accelerators, gas forming additives, waterproofing admixtures, expansion producing admixtures, shrinkage compensation admixtures, and plasticizers.
The glass reinforcement may be in the form of fibersf chopped yarns or rovings, flakes, rods, and woven or non-woven fabrics. Preferably however, the reinforcement is in the form of individual glass fibers or bundles of fibers chopped to a length of about one-fourth inch to 2 inches, most desirably abo~-t one-half inch. Fibers shorter than about .
.: ' one-fourth inch are considerably less effective as reinforce-ment, while fibers in excess of about 2 inches become entangled or fo~n balls during mixing or o~herwise do not maintain adequate dispersion throughout the cement matrix. Commer-cially available borosilicate Type E-glass may be suitably employed. However, other types of co~nercially available glass, such as the various alkali resistant types of glass may also be employed if desired. The amoùnt of glass reinforcement employed is preferably within the range of
2 to 15 parts per 100 parts of dry cement ~nderr and most desirably within the range of 4 to 7 parts.
The dry cement mi~ compositions in accordance with this invention may be mixed with water and formed into various articles, including constructlon elements for use in applications requiring high tensile or c~npressive strength, cast or extruded concrete articles such as decorative veneers, concrete panels~ concrete pipes or conduits.
T~e compositions are also particularly suitable as surface bonding CelnentS for applying to the surface of a concrete block wall and the like for bonding the blocks toyether without the necessity of mortar between the blocks as has been customarily done in the past. The surface bonding cement provides a moisture resistant, stucco appearance on the sur~ace o~ the wall and the thus bonded concrete blocks may be utili~ed for one or two stories, s1ngle and multi-family dwellings, warehouses and other commercial buildings up to two stories, below-grade basement walls, low-cost masonry units, fann buildings, and a variety of other appli-cations. When the composition is Qmployed as a surface bonding cement, it should be mixed with water to a cxe~ny consistency and applied b~ sprayiny or by trowel to the .~
surface of the stacked block or brick wall, pr~ferably about one-eighth inch thick and up to one-fourth inch thick.
Exempla~y compositions in accordance l~ith this invention are as ollows, the preferred composition being particularly suitable for use as a surface bonding cement: ;
parts by weight tbroad) (preferred) Portland cement 100 100 hydrated lime o_30 13-22 fine sand aggregate 0 300 100-160 glass reinforcement fiber 2-15 4-7 inhibitor ~Ba, Li, or Zn soluble salt) 0.002-8.0 .5-3 admixtures 1-20 1-20 To demonstrate the effectiveness of this invention, accelerated test methods were developed to quantitatively measure the reduction in alkali attack on glass fibers which is achieved by the addition of water soluble metal salts. The accelerated test specimens were subjected to electron microscopic examination of surface defects on the glass rein-forcement fibers as well as to chemical analysis of rate and quantity of glass corrosion.
In most cases, the control specimen was an alkalî resistant glass reinforcement fiber sold commercially as CEMFIL* and produced by Pilkington Brothers, Ltd. or its licensees under IJ.S. Patent No. 3,8611926.
The CEMFIL fiber is of the following composition, in molecular weight pe~centages:
SiO262% to 75%
Zr~27% to 11%
R 013% to 21%
R~O1% to 10%
Al 030% to 4%
B2~0% to 6%
Fe ~30% to 5%
C ~20% to 2%
TiO20% to 4%
*Trademark .. .. . . .
Wherein R2 represents Na2 and up to 2 mol % Li20, and R'O
is an oxide selected from the group consisting of the alkaline earth metal oxides, zinc oxide (ZnO) and manganese oxide (MnO).
The inhibitors were evaluated in combination with commercially available alkali susceptible E-glass fibers, which until now have not been recommended for use in alkali binders.
Their composition is typically as follows:
SiO2 52.6~ by weight A123 14.6 CaO 17.6 MbO 4.0 B203 6.~
Na20 1.4 K20 1. 9 Organic Sizing lo 3 100.0%
These fibers are commercially available and manufactured by Johns Manville Company as code 308 reinforcing fibers.
Example I
The CEMFIL glass and the code 308 E-glass fibers were exposed to an alkali solution of 1.0 N sodium hydroxide and the level of corrosion was determined by colorometrical quantitative analysis of the soluble silicates. In each instance 20 grams of the glass fiber was placed in polyethylene bottles with 200 ml of 1.0 N sodium hydroxide and maintained at temperatures of 75 Fo and 120 F. for periods of 7 and 28 days.
Table I gives the quantity of soluble silica of these specimens in mg/g at the specified times and temperatures.
TABLE I
soluble silica 7 days 28 davs 75~~- - 120 F. 7-5- F,cI200 (1) E-glass fiber code 308A 19.7 32.536.0 49.0 (2) E-glass fiber code 3535 8.4 41~546.0 64.0
The dry cement mi~ compositions in accordance with this invention may be mixed with water and formed into various articles, including constructlon elements for use in applications requiring high tensile or c~npressive strength, cast or extruded concrete articles such as decorative veneers, concrete panels~ concrete pipes or conduits.
T~e compositions are also particularly suitable as surface bonding CelnentS for applying to the surface of a concrete block wall and the like for bonding the blocks toyether without the necessity of mortar between the blocks as has been customarily done in the past. The surface bonding cement provides a moisture resistant, stucco appearance on the sur~ace o~ the wall and the thus bonded concrete blocks may be utili~ed for one or two stories, s1ngle and multi-family dwellings, warehouses and other commercial buildings up to two stories, below-grade basement walls, low-cost masonry units, fann buildings, and a variety of other appli-cations. When the composition is Qmployed as a surface bonding cement, it should be mixed with water to a cxe~ny consistency and applied b~ sprayiny or by trowel to the .~
surface of the stacked block or brick wall, pr~ferably about one-eighth inch thick and up to one-fourth inch thick.
Exempla~y compositions in accordance l~ith this invention are as ollows, the preferred composition being particularly suitable for use as a surface bonding cement: ;
parts by weight tbroad) (preferred) Portland cement 100 100 hydrated lime o_30 13-22 fine sand aggregate 0 300 100-160 glass reinforcement fiber 2-15 4-7 inhibitor ~Ba, Li, or Zn soluble salt) 0.002-8.0 .5-3 admixtures 1-20 1-20 To demonstrate the effectiveness of this invention, accelerated test methods were developed to quantitatively measure the reduction in alkali attack on glass fibers which is achieved by the addition of water soluble metal salts. The accelerated test specimens were subjected to electron microscopic examination of surface defects on the glass rein-forcement fibers as well as to chemical analysis of rate and quantity of glass corrosion.
In most cases, the control specimen was an alkalî resistant glass reinforcement fiber sold commercially as CEMFIL* and produced by Pilkington Brothers, Ltd. or its licensees under IJ.S. Patent No. 3,8611926.
The CEMFIL fiber is of the following composition, in molecular weight pe~centages:
SiO262% to 75%
Zr~27% to 11%
R 013% to 21%
R~O1% to 10%
Al 030% to 4%
B2~0% to 6%
Fe ~30% to 5%
C ~20% to 2%
TiO20% to 4%
*Trademark .. .. . . .
Wherein R2 represents Na2 and up to 2 mol % Li20, and R'O
is an oxide selected from the group consisting of the alkaline earth metal oxides, zinc oxide (ZnO) and manganese oxide (MnO).
The inhibitors were evaluated in combination with commercially available alkali susceptible E-glass fibers, which until now have not been recommended for use in alkali binders.
Their composition is typically as follows:
SiO2 52.6~ by weight A123 14.6 CaO 17.6 MbO 4.0 B203 6.~
Na20 1.4 K20 1. 9 Organic Sizing lo 3 100.0%
These fibers are commercially available and manufactured by Johns Manville Company as code 308 reinforcing fibers.
Example I
The CEMFIL glass and the code 308 E-glass fibers were exposed to an alkali solution of 1.0 N sodium hydroxide and the level of corrosion was determined by colorometrical quantitative analysis of the soluble silicates. In each instance 20 grams of the glass fiber was placed in polyethylene bottles with 200 ml of 1.0 N sodium hydroxide and maintained at temperatures of 75 Fo and 120 F. for periods of 7 and 28 days.
Table I gives the quantity of soluble silica of these specimens in mg/g at the specified times and temperatures.
TABLE I
soluble silica 7 days 28 davs 75~~- - 120 F. 7-5- F,cI200 (1) E-glass fiber code 308A 19.7 32.536.0 49.0 (2) E-glass fiber code 3535 8.4 41~546.0 64.0
(3) AR-glass OCF K 885 CA3.4 60.8 15,518500
(4) AR-glass CEMFIL .5 9.9 lo 533.0 It is apparent that -the alkali resistant glass fibers, while relatively resistant to alkali attack at room temperature~ are very susceptible to alkali attack at elevated temperature.
Calculating Erom the known original silica content of the fibers, the data of Table I represent a signi:Eicant amount of glass fiher corrosion, as seen from Table II.
TABLE II
28 day exposure to lN NaOH2 at 75F at 120F
Sample SiO2 Content% Glass attacked 5a~% 8.52% 9~07%
2 54% 6.83% 11.85%
10 3 62% 2042% 29.84%
4 69% 0.22% 4.78%
This example demonstrates that an effective inhibitor would be desirable not only in conjunction with E-glass reinforcing fibers, but also with the alkali resistant types of glass fibers, parti-cularly where the alkali resistant fibers are subjected to severe conditions such as elevated temperature.
Example II
The procedure of Example I was repeated with the addition of small amounts of soluble salts of barium, lithium 20 and zinc to the E-glass and alkali resistant glass fibers. The results are shown in Table TII.
TABLE III
Soluble Silicate (mg/g3 7 days 28 daYs 75F120~F 75F 120F
E-Glass Fiber JM308 no inhibitor 19.7 33.0 46.0 48.0 +19~ BaC12 8.010.7 15.0 22.3 +19~ LiC03 10.315.5 19.0 20 +1% Zn (CH3C00)2 9.8 10.2 20.0 22.8 +5% BaC12 3.35.4 5.0 14.0 AR glass Fiberno inhibitor ~ 3.3 ---- 16.0 CEMFIL +10% BaC12 ---- 0.7 ---- 1.3 E-glass Fiber Code 3535 no inhibitor ~ 25~1 ~--- 29.7 +10% BaC12 ---- 3.7 -~ 3.8 This example clearly demonstrates that bar:ium chloride, lithium carbonate, and zinc acetate, in concentrations as low as one percent, effectively inhibit alkali corrosion of both E-glass fibers and alkali resistant glass fibers.
.:
: ~ , . ,: ,. . .
:
Example III
The procedure of Example I was repeated varying the amount of barium salt used as a percent of the weight of total glass. ~he test was done only at 120. The results are shown in Table IV.
TABLE IV
Soluble Silica (mg/g) 7 days 28 days E-Glass Code 308 ~o inhibitor21.622.8 ~ 1~ BaC12 15~022.3 + 5~ BaC12 5.014.0 +10% BaC12 3.04.6 +20% saC12 2.02.5 +30~ BaC12 1.61.7 +40~ BaC12 1.31~5 ~50~ BaC12 1.42.0 +10% Ba(c2H3o)2 3-+10% BaC03 22.028.0 +10% Ba(N03)2 3.8 4.2 It will be seen that the barium chloride addition is effective at levels as low as one percent and is highly effective at levels of ten percent or greater. It will be further noted that barium carbonate, a water insoluble barium salt~ is ineffective -as an inhibitor.
Example IV
. .
~ comparison was made of the effectiveness of various levels of soluble barium chloride by boiling E-glass reinforcement fibers in a Portland cement slurry with barium chloride added thereto at levels of 0%, 1%, 5~ and 10% by weight based upon the glass fibers. After boiling for four hours, the fibers were removed from the slurry r washed~ dried, and examined for corrosion and surface pitting by scanning electron microscope at 4000X magnification. The E-glass fibers exposed to the Portland cement slurry without inhibitor showed serious surface corrosion.
However~ in those samples exposed to the slurry containing barium chloride inhibitor, no surface defects could be observed.
., ,,, ,~ , ,, ~
```
Example V
Test panels 1/8 inch thick containing E-Glass reinforcement in a Portland cement-lime binder were prepared.
sarium chloride was incorporated in three of the panels at concentrations of one percent, five percent and ten percent based upon the weight of the glass. A fourth panel serving as a control sample, contained no inhibitor. The test panels were exposed for 1,000 hours in an atlas Weather-O-Meter. This exposu~e simulates accelerated weathering under high ultraviolet ligh~ and rain cycles with an intensity of one hour equals 24 hours outdoor exposure. After exposure for 1,000 hours, simulating approximately 30 months of exposure, the glass fibers were carefully removed and examined for possible sur~ace defects by means of a scanning electron microscope at 5000X magnification.
No surface defects were noticed in the three samples containing barium chloride, while the control sample without barium chloride showed definite surface pitting.
In the specification there have been set forth preferred details of the invention, and although specific terms are employed, they are used in a generic and descriptive sense only and not for purposes o limitation.
Calculating Erom the known original silica content of the fibers, the data of Table I represent a signi:Eicant amount of glass fiher corrosion, as seen from Table II.
TABLE II
28 day exposure to lN NaOH2 at 75F at 120F
Sample SiO2 Content% Glass attacked 5a~% 8.52% 9~07%
2 54% 6.83% 11.85%
10 3 62% 2042% 29.84%
4 69% 0.22% 4.78%
This example demonstrates that an effective inhibitor would be desirable not only in conjunction with E-glass reinforcing fibers, but also with the alkali resistant types of glass fibers, parti-cularly where the alkali resistant fibers are subjected to severe conditions such as elevated temperature.
Example II
The procedure of Example I was repeated with the addition of small amounts of soluble salts of barium, lithium 20 and zinc to the E-glass and alkali resistant glass fibers. The results are shown in Table TII.
TABLE III
Soluble Silicate (mg/g3 7 days 28 daYs 75F120~F 75F 120F
E-Glass Fiber JM308 no inhibitor 19.7 33.0 46.0 48.0 +19~ BaC12 8.010.7 15.0 22.3 +19~ LiC03 10.315.5 19.0 20 +1% Zn (CH3C00)2 9.8 10.2 20.0 22.8 +5% BaC12 3.35.4 5.0 14.0 AR glass Fiberno inhibitor ~ 3.3 ---- 16.0 CEMFIL +10% BaC12 ---- 0.7 ---- 1.3 E-glass Fiber Code 3535 no inhibitor ~ 25~1 ~--- 29.7 +10% BaC12 ---- 3.7 -~ 3.8 This example clearly demonstrates that bar:ium chloride, lithium carbonate, and zinc acetate, in concentrations as low as one percent, effectively inhibit alkali corrosion of both E-glass fibers and alkali resistant glass fibers.
.:
: ~ , . ,: ,. . .
:
Example III
The procedure of Example I was repeated varying the amount of barium salt used as a percent of the weight of total glass. ~he test was done only at 120. The results are shown in Table IV.
TABLE IV
Soluble Silica (mg/g) 7 days 28 days E-Glass Code 308 ~o inhibitor21.622.8 ~ 1~ BaC12 15~022.3 + 5~ BaC12 5.014.0 +10% BaC12 3.04.6 +20% saC12 2.02.5 +30~ BaC12 1.61.7 +40~ BaC12 1.31~5 ~50~ BaC12 1.42.0 +10% Ba(c2H3o)2 3-+10% BaC03 22.028.0 +10% Ba(N03)2 3.8 4.2 It will be seen that the barium chloride addition is effective at levels as low as one percent and is highly effective at levels of ten percent or greater. It will be further noted that barium carbonate, a water insoluble barium salt~ is ineffective -as an inhibitor.
Example IV
. .
~ comparison was made of the effectiveness of various levels of soluble barium chloride by boiling E-glass reinforcement fibers in a Portland cement slurry with barium chloride added thereto at levels of 0%, 1%, 5~ and 10% by weight based upon the glass fibers. After boiling for four hours, the fibers were removed from the slurry r washed~ dried, and examined for corrosion and surface pitting by scanning electron microscope at 4000X magnification. The E-glass fibers exposed to the Portland cement slurry without inhibitor showed serious surface corrosion.
However~ in those samples exposed to the slurry containing barium chloride inhibitor, no surface defects could be observed.
., ,,, ,~ , ,, ~
```
Example V
Test panels 1/8 inch thick containing E-Glass reinforcement in a Portland cement-lime binder were prepared.
sarium chloride was incorporated in three of the panels at concentrations of one percent, five percent and ten percent based upon the weight of the glass. A fourth panel serving as a control sample, contained no inhibitor. The test panels were exposed for 1,000 hours in an atlas Weather-O-Meter. This exposu~e simulates accelerated weathering under high ultraviolet ligh~ and rain cycles with an intensity of one hour equals 24 hours outdoor exposure. After exposure for 1,000 hours, simulating approximately 30 months of exposure, the glass fibers were carefully removed and examined for possible sur~ace defects by means of a scanning electron microscope at 5000X magnification.
No surface defects were noticed in the three samples containing barium chloride, while the control sample without barium chloride showed definite surface pitting.
In the specification there have been set forth preferred details of the invention, and although specific terms are employed, they are used in a generic and descriptive sense only and not for purposes o limitation.
Claims (9)
The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. A method of making a glass reinforced cementitious material comprising the steps of adding water to a mixture of inorganic alkaline cementitious binder and glass reinforcement fibers, mixing the components and allowing the mixture to harden and cure; characterized by inhibiting degradation of the glass reinforcement fibers in the alkaline environment of the cementitious binder by adding to the mixture of inorganic cementitious binder and glass reinforcement fibers, from one half to fifty percent by weight based upon the weight of the glass reinforcement fibers of finely divided particles of a water soluble salt of a metal selected from the group consisting of barium, lithium and zinc.
2. A cement mix suitable for use in the method of Claim 1 and comprising a dry mixture of an inorganic cementitious binder containing at least one reactive alkali compound and selected from the group consisting of Portland cement, masonry cement, mixtures of Portland cement and masonry cement, and mixtures of the foregoing with hydrated lime; from two to fifteen percent by weight of descrete glass reinforcement fibers, based upon the dry weight of said bonder;
and from one-half to fifty percent by weight based upon the weight of the glass reinforcement of a water soluble salt of a metal selected from the group consisting of barium, lithium, and zinc, said salt being in finely divided particulate form and distributed throughout the cement mix.
and from one-half to fifty percent by weight based upon the weight of the glass reinforcement of a water soluble salt of a metal selected from the group consisting of barium, lithium, and zinc, said salt being in finely divided particulate form and distributed throughout the cement mix.
3. A method of making a surface bonded wall comprising the steps of applying a coating of a surface bonding cement over at least one surface of an assembly of stacked concrete blocks and allowing the cement coating to harden and cure and serve to bond the blocks together without the necessity of mortar between the blocks, and wherein said coating of surface bonding cement comprises an inorganic cementitious binder containing at least one reactive alkali compound, glass reinforcement fibers distributed throughout the binder, and fine sand aggregate also distributed throughout the binder; characterized by inhibiting degradation of the glass reinforcement fibers in the alkaline environment of the cementitious binder by adding to the mixture of inorganic cementitious binder, glass reinforcement fibers, and fine sand aggregate, from one-half to fifty percent by weight based upon the weight of the glass reinforcement fibers of finely divided particles of a water soluble salt of a metal selected from the group consisting of barium, lithium and zinc.
4. A cement mix suitable for use in the method of Claim 3, and comprising:
5. The method according to Claims 1 or 3 wherein said water soluble salt comprises the chloride, carbonate or acetate salt of said metal.
6. The method according to Claims 1 or 3 wherein said water soluble salt comprises barium chloride.
7. The method according to Claims 1 or 3 wherein said water soluble salt comprises zinc acetate.
8. The method according to Claims 1 or 3 wherein said water soluble salt comprises lithium carbonate.
9. The method according to Claims 1 or 3 wherein the glass reinforcement fibers comprise ordinary alkali susceptible E-glass fibers.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/832,013 US4115135A (en) | 1976-07-16 | 1977-09-09 | Composition and method for producing glass reinforced cement products |
| US832,013 | 1977-09-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1094111A true CA1094111A (en) | 1981-01-20 |
Family
ID=25260427
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA300,778A Expired CA1094111A (en) | 1977-09-09 | 1978-04-10 | Composition and method for producing glass reinforced cement products |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS5443917A (en) |
| CA (1) | CA1094111A (en) |
| GB (1) | GB1602241A (en) |
| NZ (1) | NZ186950A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56165502U (en) * | 1980-05-13 | 1981-12-08 | ||
| JPS56162052A (en) * | 1980-05-19 | 1981-12-12 | Yokogawa Hokushin Electric Corp | Measuring device for contamination load quantity |
| US5803960A (en) * | 1997-01-17 | 1998-09-08 | The Trustees Of Columbia University In The City Of New York | Glass formula for avoiding ASR |
| CN113192032A (en) * | 2021-04-29 | 2021-07-30 | 东南大学 | Prediction and evaluation method for whiskering uniformity of glass fiber reinforced cement product based on microbial whiskering resistance |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51115530A (en) * | 1975-04-03 | 1976-10-12 | Kubota Ltd | Method of manufacturing fiber glass reinforced cement molded products |
| JPS5253931A (en) * | 1975-10-29 | 1977-04-30 | Fuji Fibre Glass Co Ltd | Fibrous glass reinforced polymer cement compound |
| JPS5253930A (en) * | 1975-10-29 | 1977-04-30 | Fuji Fibre Glass Co Ltd | Fibrous glass reinforced cement compound |
-
1978
- 1978-04-10 CA CA300,778A patent/CA1094111A/en not_active Expired
- 1978-04-12 NZ NZ18695078A patent/NZ186950A/en unknown
- 1978-04-14 GB GB1482178A patent/GB1602241A/en not_active Expired
- 1978-04-18 JP JP4622578A patent/JPS5443917A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5443917A (en) | 1979-04-06 |
| GB1602241A (en) | 1981-11-11 |
| JPS5648454B2 (en) | 1981-11-16 |
| NZ186950A (en) | 1979-06-19 |
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