JPH0597495A - High strength composite material - Google Patents

Abstract

PURPOSE:To provide a high strength inorg. hardened body having excellent flame resistance. CONSTITUTION:A compsn. consisting of water granulated blast furnace slag, an alkali stimulant, a water-soluble polymer, a superfine powdery substance, org. short fibers and water is kneaded, molded and wet-cured to obtain an inorg. hardened body.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a high-strength composite material containing granulated blast furnace slag as a main component. More specifically, it relates to a high-strength composite material that can be used as a construction material, an interior material as a construction member, an exterior material, a structural material, and the like.

[0002]

2. Description of the Related Art Cement represented by Portland cement is used in various fields, mainly in the field of construction, because it is inexpensive and can develop design strength relatively easily. However, in recent years, there has been a demand for higher strength of hardened cement products. As a method of solving this problem of strengthening, Density Actieselsk AB of Denmark is developing ultra-dense cement. However, the hardened product made from this ultra-dense cement has a high compressive strength of about 1500 Kgf / cm ² , but not so much a bending strength of 200 Kgf / c 2.
It is about m ² . As for the hardened cement with high bending strength, ICI of the United Kingdom has a bending strength of 1800.
We have developed a high strength material as high as Kgf / cm ^2, but have the problems that expensive alumina cement is used as the cement and that the bending strength is large, but the water resistance is poor and the field of use is limited. is doing.

[0003]

DISCLOSURE OF THE INVENTION As a result of investigations made by the present inventors to solve the above-mentioned problems, the bending strength is high,
Moreover, we have developed an inorganic composite material with excellent water resistance and have already applied for a patent. However, this inorganic composite material has high flexural strength and is excellent in water resistance, but it is dense, so when it is supported by a flame such as a burner and is rapidly heated, the part exposed to the flame peels off. Or it will collapse (below,
These are called "flame-resistant phenomena").

[0004]

Means for Solving the Problems The inventors of the present invention have made extensive studies to solve the above-mentioned problems, and as a result, achieved the present invention. That is, the present invention is (1) kneading and molding a composition comprising granulated blast furnace slag, an alkali stimulant, a water-soluble polymer, an ultrafine powdery substance, an organic short fiber, and water, followed by wet curing. The high-strength composite material, (2) the water-soluble polymer is poly (meth) acrylate, and / or carboxymethylcellulose. With a poly (meth) acrylic acid salt having an average molecular weight of 20,000 or more. The high-strength composite material according to (1) above, or (4) the organic short fiber is pulp, polypropylene fiber or vinylon fiber, (1), (2) or (3).
(5) The high-strength composite material according to (1), (2), (3) or (4) above, wherein the ultrafine powdery substance is silica fume.

The present invention will be described in detail. The granulated blast furnace slag used has a Blaine value of 2000 cm ² / g or more, preferably 3000 cm ² / g or more.

The water-soluble polymer to be used is not particularly limited, but fine particles are preferable because it is preferable that the water-soluble polymer is uniformly and rapidly dissolved in the kneading system in a short time. The following polymers can be used as the water-soluble polymer.

(1) Water-soluble polymers having a carboxyl group and / or an amide group in the molecule, or salts thereof.

Α-Hydroxy-polyacrylic acid, or a salt thereof, and homopolymers or copolymers of the following monomers as raw materials, or salts thereof.

(Meth) acrylic amide type monomers such as acrylic amide, N, N-dimethyl acrylic amide, N-methyl acrylic amide;

(Meth) acrylic acid such as (meth) acrylic acid, sodium (meth) acrylate, potassium (meth) acrylate, lithium (meth) acrylate, 2-hydroxyethyl (or propyl) (meth) acrylate Monomer: Vinyl monomer such as N-vinylpyrrolidone, vinyl methyl ether, styrene sulfonic acid (or sodium salt or potassium salt thereof). (Here, (meth) acrylic acid means acrylic acid and / or methacrylic acid, and so on.)

(2) Cellulose derivatives Hydroxypropylmethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose.

(3) Polyvinyl acetate derivative Partially hydrolyzable polyvinyl acetate, cationized polyvinyl acetate, anionized polyvinyl acetate.

(4) Soluble starch.

(5) Polyethylene oxide.

(6) (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, styrene, ethylene,
A copolymer of propylene and the like and the water-soluble monomer described in (1) above.

Among these, preferred are poly (meth) acrylic acid salts such as sodium poly (meth) acrylate, potassium poly (meth) acrylate, etc., and carboxymethyl cellulose, and most preferred are poly (meth) acrylic acid. It is an acrylate. These poly (meth) acrylic acid salts may have any average molecular weight, but are preferably 20,000 or more, more preferably 50,000.
An average molecular weight of 0 or more, most preferably 100,000 or more is used.

The amount of these water-soluble polymers to be used is usually 0.5 to 12%, preferably 1 to 8% by weight, based on the total amount of granulated blast furnace slag and ultrafine powder. When the amount of the water-soluble polymer used is less than 0.5%, the mixture cannot be kneaded, or even if it is formed, the moldability of the subsequent step tends to be poor. On the other hand, if it exceeds 12%, the stability of the hydrated product to water tends to deteriorate.

Specific examples of the alkali stimulants that can be used include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide; alkali metal hydroxides such as sodium carbonate, potassium carbonate and lithium carbonate. Carbonate; alkali metal bicarbonate such as sodium bicarbonate, potassium bicarbonate, lithium bicarbonate; magnesium hydroxide,
Alkaline earth metal hydroxides such as calcium hydroxide;
Alkaline earth metal oxides such as calcium oxide and magnesium oxide; sodium pyrophosphate, potassium pyrophosphate,
Dipotassium phosphate, tripotassium phosphate, trisodium phosphate,
Examples thereof include sodium metasilicate and potassium metasilicate. Among these alkali stimulants, sodium hydroxide, sodium carbonate and sodium metasilicate are preferred examples.

The amount of these alkali stimulants used in the granulated blast furnace slag depends on the alkaline strength of the alkali stimulants,
Although it depends on the average particle size of the granulated blast furnace slag and the amount of water used, it is about 0.1 to 5%, preferably 0.1% to the total amount of the granulated blast furnace slag and the ultrafine powder substance. 2-3
% (Weight ratio). The amount of alkali stimulant used is 0.
If it is less than 1%, the kneaded-molded product does not cure due to wet curing, or even if it does, it takes a long time for wet curing, which is industrially disadvantageous. On the other hand, if the amount of the alkali stimulant used exceeds 5%, the curing will be too fast and the curing may start during the kneading-molding process.

Next, as the ultrafine powdery substance, one having an average particle size which is substantially the same as that of the granulated blast furnace slag, preferably one order smaller than that, and more preferably two orders smaller than that is used. .. The average particle size of the ultrafine powder is preferably 10 μm or less, more preferably 0.01 to 5 μm.
m, and most preferably 0.05 to 1 μm.
The average particle size of the ultrafine powder material is preferably 1/2 to 1/1000 of the average particle size of the granulated blast furnace slag. Examples of specific ultrafine particles that can be used are silica fume, fly ash, silica sand, silica stone powder, clay, talc,
Examples include kaolin, calcium carbonate, ground ceramics, slowly cooled blast furnace slag grounds, titania, zirconia, alumina, silica, and the like.

Among these, silica fume is a particularly preferable example. The proportion of these ultrafine particles in the total amount of granulated blast furnace slag and ultrafine particles is
Usually 2 to 50%, more preferably 5 to 30% (weight ratio)
Will be used in an amount.

The organic short fibers used in the present invention are preferably in the form of chopped fibers, but may also be in the form of fiber aggregates such as nets, rods, mats, and woven fabrics. , Vinylon fiber, pulp, polyethylene fiber, polypropylene fiber, aramid fiber, polyester fiber, and the like. Preferred of these are vinylon fibers, pulp, and polypropylene fibers. These organic short fibers may be used alone or in combination of two or more kinds. The amount of short organic fibers used is 0.2 to 10%, preferably 0.5 to 7%, based on the total amount of granulated blast furnace slag and ultrafine powder. If the amount of organic short fibers used is less than 0.2%,
The object of the present invention is not enough to eliminate the flame resistance phenomenon, and if it exceeds 10%, not only the cost is disadvantageous, but also the kneading process tends to be difficult.

The amount of water used for obtaining the high-strength inorganic composite material of the present invention is as follows: type and amount of water-soluble polymer, type and amount of alkali stimulant, type and amount of ultrafine powder, And, depending on the type and amount of organic short fibers, it must be determined so that the mixture exhibits good kneading properties,
Approximately 1 for the total amount of granulated blast furnace slag and ultrafine powder
It is 0 to 45, preferably 15 to 40%.

In the present invention, it is also possible to use the fine aggregate used in the mortar production in the cement field.
The smaller the particle size of the fine aggregate used, the greater the bending strength of the high-strength composite material of the present invention obtained by wet curing. Generally, fine aggregate having a particle size of 100 to 1000 μm is preferable. Specific examples include silica sand, silica stone powder, slowly cooled slag powder, ferrochrome slag, crushed ceramic products, crushed brick products, and anti-fire stones.

In addition, in order to control the time until the hydration reaction starts in the manufacturing process, organic acids such as gluconic acid, tartaric acid, malonic acid, succinic acid, maleic acid, fumaric acid, malic acid, or the like. Salt, glucose, fructose, sucrose,
It is also possible to add sugars such as maltose and lactose.

Next, a general method for producing the high-strength inorganic composite material of the present invention will be described. First, granulated blast furnace slag, a water-soluble polymer, an ultrafine powdery substance, an alkali stimulant (the alkali stimulant is preferably dissolved in water and mixed after mixing powder components), and organic short fibers. , An oscillating mixer such as an Omni mixer (Chiyoda Giken Kogyo Co., Ltd.),
Put in a planetary mixer and mix powder. Next, a predetermined amount of water or an alkaline solution in which an alkaline stimulant is dissolved is added to this mixture, and further mixed (coarse kneading). Next, the kneading is started, but it is preferable to use an apparatus capable of giving a strong shearing force to the coarse kneaded product. For example, a roll kneader, a Banbury mixer, a wet Banbury mixer, a mixing roll, a bag mill, a pressure kneader, a screw extruder, a kneader ruder, or the like is used, and kneading is performed until the kneaded product has a clay-like shape.

The molding machine is also not particularly limited, and calender rolls, (low to high) pressure presses, and (vacuum) extruders are generally used. Especially a method that can be molded under reduced pressure,
For example, when a vacuum extruder or a vacuum press is adopted, a hydrated cured product having larger bending strength and less variation in bending strength physical properties can be obtained, which is preferable. After molding,
Move to wet curing. The wet curing needs to be performed at least in a high-humidity atmosphere in which the water content in the kneaded-molded product does not evaporate. Generally, relative humidity is 80% or more, preferably 9
It is carried out in an atmosphere of 0% or more, more preferably 100%.

Further, in such a high humidity atmosphere, the molded body may be further put in a container or bag which is impermeable to water,
Alternatively, the wet curing may be performed by a method of preventing evaporation of water in the molded body by sandwiching the molded body between a plastic plate, a plastic film, and a metal plate.
It is also possible to carry out curing in water by immersing the molded body in the initial stage of wet curing in water.

In the present invention, the higher the wet curing temperature, the quicker the curing of the kneaded-molded product, but generally a temperature of room temperature to 100 ° C. is used. Further, steam may be used for autoclave treatment at a temperature of 100 ° C or higher. The time for wet curing depends on the type and amount of the alkaline stimulant used and the conditions for hydration hardening, but is generally about half a day to 5 days. Since the cured product after wet curing contains water, it is preferable to dry such a cured product. The drying temperature can usually be freely selected from room temperature to 100 ° C.

[0030]

EXAMPLES The present invention will be described in more detail with reference to Examples, but it goes without saying that the present invention should not be limited thereto.

Example 1 90 parts of granulated blast furnace slag (manufactured by Nippon Steel Chemical Co., Ltd .; Essment (Blaine value: 4000 cm ² / g)), 10 parts of silica fume (average particle size 0.14 μm), and poly as a water-soluble polymer 3 parts of sodium acrylate (manufactured by Nippon Kayaku Co., Ltd .; Panakayaku B) and 3 parts of pulp as organic fibers were put into an omni-mixer (manufactured by Chiyoda Giken Kogyo Co., Ltd.), which is a rocking type mixer, and powder-mixed. Next, an aqueous solution prepared by dissolving 1.0 part of sodium hydroxide in 20 parts of water as an alkali stimulant was added to this powder mixture, and further mixed (coarse kneading).

The obtained crude kneaded product was kneaded with a two-roll kneader for 4 minutes under high shearing force. The kneaded product is clay-like, and is a vacuum extruder (Honda Iron Works Co., Ltd .; HDE-2).
The mold was extruded into a plate having a width of 10 cm and a thickness of 4 mm under a reduced pressure of 740 mmHg. Put a vinyl sheet on this extruded plate, leave it at room temperature for 1 day (pre-curing) in a state where the water content in the molded body does not scatter, and then wet for 2 days in a constant temperature and humidity chamber at 90 ° C and a relative humidity of 100%. Cure
A high strength composite material of the present invention was obtained.

From this high-strength composite material, a length of 8c was obtained as a sample for bending physical property measurement and flame resistance test measurement.
A large number of small pieces each having a width of 1.5 cm and a width of 1.5 cm were cut out, and some of the samples were dried in a dryer at 60 ° C. for 24 hours. The results of these three-point bending tests are shown below. The three-point bending test is performed by Tensilon (manufactured by Orientec Co., Ltd .; UTM-250).
0) was used, and the span was 6 cm, and the bending speed was 1 mm / min. Further, in the flame resistance test, the sample was held over an ignited experimental burner, and it was observed whether or not the small pieces were separated from the cured body.

After wet curing After drying Bending strength Kgf / cm ² 405 590 Bending elastic modulus Kgf / cm ² , * 10 ⁴ 25.8 27.1 No flame resistance Phenomenon None None 30 ° C., 2N caustic soda solution was used. The intrinsic viscosity [η] of the sodium polyacrylate used in this example measured by a capillary viscometer was 0.71 and the average molecular weight calculated by the following conversion formula was 2.04 × 10 ⁶ . .. Conversion formula ─── [η] = 8 × 10 ^-8 Mw ^1.1

Example 2 4 parts of potassium polyacrylate as a water-soluble polymer, 2 parts of sodium metasilicate as an alkali stimulant, and 1 part of water
8 parts, vinylon fiber (made by Kuraray Co., Ltd .; fiber length 6 mm) as organic short fiber 1 part and polypropylene fiber (Co., Ltd.)
A high-strength composite material of the present invention was obtained by performing the same operation as in Example 1 except that 2 parts of TF-6 made by Tezac and a fiber length of 6 mm) were used. The results of the three-point bending test and the flame resistance test are shown below. In addition, potassium polyacrylate is 35% (weight)
The potassium acrylate aqueous solution was prepared according to a conventional method using potassium persulfate as a polymerization initiator. The intrinsic viscosity [η] of the obtained potassium polyacrylate was 0.69 (Example 1
Was measured in the same manner as in (1), and was almost equivalent to 0.71 of sodium polyacrylate used in Example 1, and was equivalent in terms of molecular weight. That is, when the average molecular weight of the potassium polyacrylate used in this example was calculated from the conversion formula described in Example 1, it was 2.02 × 10 ⁶ .

After wet curing After drying Flexural strength Kgf / cm ² 420 610 Flexural modulus Kgf / cm ² , * 10 ⁴ 26.3 27.2 Anti-flame phenomenon None None

Example 3 As a water-soluble polymer, 7 parts of carboxymethyl cellulose (Daiichi Kogyo Seiyaku Co., Ltd .; serogen BSH-12), 1.5 parts of sodium hydroxide as an alkali stimulant, and 2 parts of water were used.
5 parts, aramid fiber as an organic fiber (manufactured by Teijin Ltd .;
Technora, 1.5 parts of fiber length 6 mm) and 4 parts of pulp, and 40 parts of ferrochrome slag (manufactured by Japan Magnetic Separation Co., Ltd .; NJ Sand No. 7) as fine aggregate were used. The operation was performed to obtain the high-strength composite material of the present invention. The results of the three-point bending test and the flame resistance test are shown below.

After wet curing After drying Flexural strength Kgf / cm ² 360 630 Flexural modulus Kgf / cm ² , * 10 ⁴ 25.8 27.0 Anti-flame phenomenon None None

Example 4 5 parts of the sodium polyacrylate used in Example 1 as a water-soluble polymer, 1.2 parts of sodium hydroxide as an alkali stimulant, and 4.5 parts of pulp as an organic short fiber,
The high-strength composite material of the present invention was obtained by the same procedure as in Example 1 except that 50 parts of No. 7 silica sand was used as the fine aggregate. The results of the three-point bending test and the flame resistance test are shown below.

After wet curing After drying Flexural strength Kgf / cm ² 310 560 Flexural modulus Kgf / cm ² , * 10 ⁴ 23.2 24.4 Anti-flame phenomenon None None

Comparative Example 1 A high-strength composite material was obtained by the same procedure as in Example 1 except that pulp was not used. The results of the three-point bending test and the flame resistance test are shown below.

After wet curing After drying Flexural strength Kgf / cm ² 400 575 Flexural modulus Kgf / cm ² , * 10 ⁴ 26.2 27.4 Flame resistance Yes Yes

[0043]

EFFECTS OF THE INVENTION It has been possible to develop a composite material which is made of inexpensive granulated blast furnace slag as a main raw material and has high strength and excellent resistance to flame.

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Claims (5)

[Claims] 1. A high-strength composite obtained by kneading and molding a composition comprising granulated blast furnace slag, an alkali stimulant, a water-soluble polymer, an ultrafine powdery substance, organic short fibers, and water, and then wet curing. material. 2. The high-strength composite material according to claim 1, wherein the water-soluble polymer is poly (meth) acrylic acid salt and / or carboxymethyl cellulose. 3. The water-soluble polymer has an average molecular weight of 20,000.
The high-strength composite material according to claim 1, which is the above poly (meth) acrylate. 4. The high-strength composite material according to claim 1, 2 or 3, wherein the organic short fibers are pulp, polypropylene fibers or vinylon fibers. 5. The high-strength composite material according to claim 1, 2, 3, or 4, wherein the ultrafine powdery substance is silica fume.