JPH07144953A - Hydraulic blended material and production of hydraulic hardened body - Google Patents

Abstract

PURPOSE:To obtain a blended body capable of securing excellent workability and sufficient working time and obtaining a dense high strength hardened body in the extremely low ratio of water to a binder by using a polycarboxylic acid based as a water reducing agent in a blended material containing the binder, an aggregate, the high performance water reducing agent and water. CONSTITUTION:The hydraulic blended material containing the binder, the aggregate, the polycarboxylic acid based water reducing agent and water is kneaded at the weight ratio of water to binder of 0.10-0.20 and molded. The polycarboxylic acid based high performance water reducing agent shows extremely excellent water reducing and' fluidizing action at the extremely low ratio of water to the binder of <=0.2. As a result, in the extremely low ratio of water to the binder such as <=0.20, excellent workability and sufficient working time are secured and the dense high strength hardened body is obtained without using a special molding method such as press molding.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a hydraulic compound and a hydraulic cured product, and in particular, for mortar, concrete, etc. which can be kneaded at an extremely low water / binder ratio and exhibit high strength. The present invention relates to a hydraulic compound and a method for producing a hydraulic cured product.

[0002]

2. Description of the Related Art Recently, 1 has been applied to mortar, concrete, etc.
High strength exceeding 000 kgf / cm ² is being demanded, and high strength is becoming more important even for short-term age such as age 3 days. For high strength in mortar, concrete, etc., it is essential to reduce the water / binder weight ratio. Conventionally, by using a high-performance water reducing agent such as naphthalene sulfonic acid type or amino sulfonic acid type and silica fume with bearing effect, it is possible to reduce the water / binder weight ratio and obtain a considerably high strength cured product. Has been.

However, in order to obtain a high-strength cured product by further reducing the water / binder weight ratio, water / binder is particularly preferable.
When the binder weight ratio is 0.20 or less and the fine aggregate / binder weight ratio is 0.20 or more, a markedly kneaded state or an excessively viscous state occurs, or the fluid flows rapidly with time. It was not possible to secure good workability and sufficient work time, such as the phenomenon of loss of sex.

[0004]

As described above, in a high-performance water reducing agent such as a naphthalenesulfonic acid-based or aminosulfonic acid-based water reducing agent, water reduction at an ultra-low water / binder weight ratio of 0.20 or less,
The fluidization effect is not sufficient, and the addition of silica fume causes an excessive increase in viscosity, so there is a limit to obtaining a high strength cured product by ordinary kneading work, and for those requiring higher strength At present, high strength is secured by a special molding method such as pressure molding.

Therefore, an object of the present invention is to ensure good workability and sufficient working time at an ultra-low water / binder ratio such as a water / binder weight ratio of 0.20 or less. It is an object of the present invention to provide a hydraulic compound and a method for producing a hydraulic cured product that can obtain a dense high-strength cured product with few defects without using a special molding method such as pressure molding.

[0006]

In order to achieve the above-mentioned object, the hydraulic composition of the present invention comprises a binder, an aggregate, a polycarboxylic acid type superplasticizer, and water,
The water / binder weight ratio is 0.10 to 0.20 (claim 1), the binder has a hydraulic modulus of 2.20 or more, a Blaine specific surface area of 4000 cm ² / g or more, and a residual value on a 30 μm sieve. 1
It is Portland cement adjusted to 0 to 20% by weight (claim 2), the binder has a hydraulic modulus of 2.20 or more, a Blaine specific surface area of 4000 cm ² / g or more, and a residue value on a 30 μm sieve of 10 to 20% by weight. 80% by weight or more of Portland cement adjusted to 100% and a Blaine specific surface area of 10000 cm
^{It is} composed of 20 parts by weight or less of ultrafine powder of ² / g or more (claim 3), and the number of particles that pass through a sieve of 0.15 mm is 5
It contains fine aggregate whose particle size is adjusted to be less than or equal to wt%, the fine aggregate / binder weight ratio is 0.20 or more (Claim 4), and the fine aggregate has a residue on the sieve of 2.0 mm. The particle size is adjusted so that the value is 5% by weight or less (claim 5),
The fine aggregate is a spherical aggregate (claim 6), and the binder 10
It is characterized by containing 2.0% by weight or less of a hydration accelerator with respect to 0 part by weight (claim 7), and the hydration accelerator being calcium nitrite (claim 8).

Further, according to the method for producing a hydraulically cured product of the present invention, a binder, an aggregate, a polycarboxylic acid type high-performance water reducing agent, and a hydraulic compound containing water are added to a water / binder weight ratio. Kneading and mixing at a ratio of 0.10 to 0.20 (claim 9) and kneading at atmospheric pressure or lower (claim 1)
0), the binder has a hydraulic modulus of 2.20 or more, a Blaine specific surface area of 4000 cm ² / g or more, and a residual value on a 30 μm sieve of 10 to 10.
It is Portland cement adjusted to 20% by weight (claim 11), the binder has a hydraulic modulus of 2.20 or more, a Blaine specific surface area of 4000 cm ² / g or more, and a residual value on the 30 μm sieve of 10 to 20% by weight. 80 parts by weight or more of the adjusted Portland cement and a Blaine specific surface area of 10000 cm ²
/ G or more and 20 parts by weight or less of ultrafine powder (claim 12), and the aggregate has 5 particles that pass through a 0.15 mm sieve.
It contains fine aggregate whose particle size is adjusted to be less than or equal to wt%, the fine aggregate / binder weight ratio is 0.20 or more (claim 13), and the fine aggregate has a residue on the sieve of 2.0 mm. The particle size is adjusted so that the value is 5% by weight or less (claim 1
4) The fine aggregate is a spherical aggregate (claim 15), and the hydraulic composition contains 2.0% by weight or less of a hydration accelerator with respect to 100 parts by weight of the binder (claim 15). Item 16), wherein the hydration accelerator is calcium nitrite (Claim 17). Hereinafter, the present invention will be described in detail.

In the present invention, the binder is a normal, early strength,
Various portland cements such as super early strength, moderate heat, sulfate resistance, white, etc. can be used, but in consideration of hydration reactivity, fluidity and strength development in a short-term age, the water hardness is 2.20. With the above, the Blaine specific surface area of 4000 cm ² / g
As described above, Portland cement adjusted to have a residual value on the sieve of 30 μm of 10 to 20% by weight can be preferably used. Hydraulic modulus 2.
When it is less than 20 and the Blaine specific surface area of 4000 cm ² / g, sufficient strength development cannot be obtained in a short-term age. In addition, the residual value on the 30 μm sieve is in consideration of both fluidity and strength development. When the amount of particles remaining on the 30 μm sieve is less than 10% by weight, sufficient fluidity cannot be obtained. ,
If this content exceeds 20% by weight, the strength developability will decrease and the coarse cement particles will interfere with the fine particles in the fine aggregate, resulting in a decrease in fluidity.

[0009] aforementioned binder, Blaine specific surface area of 20 parts by weight of Portland cement 10000 cm ²
It can be used by replacing it with an ultrafine powder having an amount of / g or more. The ultrafine powder enhances the fluidity by the bearing effect and makes the hydraulically hardened body dense by the microfiller effect, which greatly contributes to the strength development. When the Blaine specific surface area is less than 10000 cm ² / g, the ultrafine powder cannot sufficiently obtain the bearing effect and the microfiller effect, but when the Blaine specific surface area is 10000 cm ² / g or more, the shape and components are It can be used without limitation, and for example, silica fume, aerosil, calcium carbonate, blast furnace slag, fly ash and the like are preferably used. If the substitution amount of the ultrafine powder for Portland cement exceeds 20 parts by weight, the fluidity is lowered, which is not preferable, and if it is less than 5 parts by weight, almost no effect is obtained.

Next, aggregates include ordinary aggregates such as sand, gravel, and crushed stone used for ordinary mortar and concrete, metal aggregates such as iron and stainless steel, ceramic aggregates such as alumina, and expansion. It can be used regardless of the type of various aggregates such as lightweight aggregates such as shale, but in consideration of fluidity in particular, the particle size is adjusted so that the particles passing through a 0.15 mm sieve are 5% by weight or less. It is preferable that the fine aggregate is included. By adjusting the particle size in this way, it is possible to prevent the fine aggregate particles from interfering with the coarse particles in the cement and obtain good fluidity.

Further, the fine aggregate is adjusted in such a manner that the particles remaining on the 2.0 mm sieve are adjusted to have a particle size of 5% by weight or less, so that the clearance between the mold and the adhered parts is small (for example, Even if it is about 5 to 10 mm), it becomes possible to easily fill the mortar.

[0012] Further, in the above-mentioned aggregate, when the above-mentioned particle size is adjusted, by using spherical aggregate as fine aggregate, the fluidity can be remarkably improved, which is very preferable. The spherical aggregate here is usually one obtained by melting metal or ceramics, then scattering and cooling by atmospheric pressure and cooling, and its shape is a rounded spherical shape or something close to it, which constitutes the aggregate. There are no component restrictions.
As this type of spherical aggregate, quenching products of converter slag and blast furnace slag, iron spheres, stainless spheres, glass spheres, ceramic spheres such as alumina and zircon mullite can be preferably used, and fine aggregate / bonding material weight It is used so that the ratio becomes 0.20 or more.

Next, the polycarboxylic acid-based high-performance water reducing agent used in the present invention contains a polycarboxylic acid and / or a polycarboxylic acid salt as a main component, and other known naphthalenesulfonic acid-based or Compared with high performance water reducing agents such as aminosulfonic acid type, the water reducing and fluidizing effects at an extremely low water / binder weight ratio of 0.20 or less are extremely good. In particular, it has excellent compatibility with Portland cement whose hydraulic modulus is adjusted to 0.20 or more, and has the effect of significantly improving water reduction and fluidity without impairing hydration reactivity in short-term age. .

As the polycarboxylic acid-based high-performance water-reducing agent, one or more polymers of a polymerizable monomer containing a carboxyl group or an anhydride thereof, or a polymerizable monomer containing a carboxyl group is used. A compound having a mean molecular weight of 500 to 50,000, which is a polymer of one or more kinds of the isomer or an anhydride thereof and another polymerizable monomer or a salt thereof, is preferably used. Specifically, polyacrylates, polymethacrylates, copolymers of acrylic acid and allyl ether, α
-Copolymers of olefin and ethylenically unsaturated dicarboxylic acid, water-soluble salts such as partially esterified products, partially amidated products and partially imidized products thereof are exemplified, and as typical ones currently marketed,・ SP Company, SP-8 series, HP-1 manufactured by Takemoto Yushi Co., Ltd.
1 series, Work 500 manufactured by Nippon Zeon Co., Ltd., 100PHX manufactured by Denka Grace Co., Ltd. and the like are preferably used, but not limited thereto.

The amount of the polycarboxylic acid type high-performance water reducing agent shown above is adjusted in consideration of Portland cement for adjusting the particle size, the aggregate, and the required water reducing effect. 0.1 to 10% by weight, preferably 1 to 5% by weight is added. If it is less than 0.1% by weight, the water-reducing effect is substantially absent, and if it is added in excess of 10% by weight, the effects of improving the water-reducing property and the fluidity reach a ceiling.

In addition to the above-described compounding ingredients, the present invention also provides various compounding agents and reinforcing materials such as quick-hardening / quick-setting agents, high-strength admixtures, chemical admixtures ordinarily used in cement, mortar and concrete. It is also possible to use various fibers and steels. In particular, the addition of calcium nitrite as a hydration accelerator has the effect of enhancing the hydration reaction of Portland cement and shortens the time during which good fluidity can be maintained, but it provides fast hardening, so The strength within can be greatly increased. The amount of calcium nitrite added is preferably 2.0 parts by weight or less with respect to 100 parts by weight of the binder, because the more the amount of calcium nitrite is added, the shorter the time during which fluidity can be maintained.

In the present invention, the water / binder weight ratio is 0.10 to 0.20 by combining the binder, aggregate and polycarboxylic acid type high performance water reducing agent described above.
To secure good workability and sufficient working time by ordinary cast molding or vibration compaction molding without using a special molding method such as pressure molding with an ultra-low water / binder ratio. You can In this case, there is no limitation on the mixing and kneading method of the above respective components, and any method may be used as long as it can be uniformly mixed and kneaded, but when kneading is performed under the atmospheric pressure in the mixer, kneading that causes strength reduction It prevents air entrainment during mixing and further enables reduction of the water / binder ratio by evaporation of water under reduced pressure. Pressure is
The pressure is preferably 0.5 atm or less, but the effect can be obtained at the atmospheric pressure or less. The order of adding the components is not particularly limited.

Next, the kneaded product is cured, and various curing methods can be applied for curing, and any of normal temperature curing, high temperature curing, normal pressure steam curing, and high temperature and high pressure curing can be adopted.
If necessary, these can be combined to obtain a high-strength hydraulic cured product.

[0019]

As described above, in order to obtain high strength in mortar, concrete, etc., it is necessary to reduce the water / binder weight ratio. This invention uses a combination of a binder, an aggregate, and a polycarboxylic acid-based high-performance water-reducing agent, and particularly, has a hydraulic modulus of 2.20 or more, a Blaine specific surface area of 4000 cm ² / g or more, and a residual value on a 30 μm sieve. 10 to
Portland cement adjusted to 20% by weight, 0.15
Preventing interference between Portland cement particles and aggregate particles by combining fine aggregate with a particle size adjusted so that the amount of particles passing through a sieve of mm is 5% by weight or less, and a polycarboxylic acid-based high-performance water reducing agent. These three factors act synergistically such as extremely good compatibility with a polycarboxylic acid type high-performance water reducing agent, and a water / binder weight ratio of 0.20 or less and a fine aggregate / binder weight ratio of 0.20. Under the extremely severe conditions described above, good workability and sufficient work time can be secured, and a high-strength hydraulic cured product can be obtained.

[0020]

EXAMPLES The present invention will be described below with reference to examples and comparative examples. In Examples and Comparative Examples, mortar was prepared according to the following blending materials and blending ratios, followed by JIS, R5201.
The mortar flow test and the compressive strength test were performed according to the above. The results are shown in Table 1.

[0021]

[Table 1]

Examples 1 to 3 and Comparative Example 1 As a binder, a hydraulic modulus of 2.22 and a Blaine specific surface area 42
30 cm ² / g, 30 μm 100 parts by weight of Portland cement adjusted to a residual value of 14.6% by weight on a sieve, 0.15 mm as an aggregate, particle size adjusted to a passing value of 2.2% by weight under a sieve (2.5 mm on a sieve) 50 parts by weight of natural Ogasayama sand (residual value 14.6% by weight) (fine aggregate / binder ratio 50% by weight), as a polycarboxylic acid-based high-performance water reducing agent, Takemoto Yushi Co., Ltd.
Water was added to 2 parts by weight of HP-11 (N) manufactured at a mixing ratio shown in Table 1, the pressure in the mixer was adjusted to 1 atm, and the mixture was kneaded.
It was mortar. As shown in Table 1, each of the present inventions maintains good fluidity up to 30 minutes and has a water / binder ratio of 1
Even with 9% by weight (Example 3), 900 kgf /
Although a compressive strength of cm ² or more was obtained, when the water / binder ratio was 21% by weight (Comparative Example 1), the compressive strength on the 3rd day was about 700 kgf / cm ² .

Examples 4, 5 and 6 The fine aggregate / binder ratio was 25% by weight (Example 4), and as a polycarboxylic acid-based high-performance water reducing agent, SP manufactured by NMB Co., Ltd. was used. -8HS 2 parts by weight (Example 5), as aggregate, 0.15 mm, passing value under sieve of 4.6% by weight, 2.5 mm
Mortar was kneaded under the same conditions as in Example 2 except that natural Ogasayama sand (Example 6) whose particle size was adjusted to a sieve residue value of 4.3% by weight was used. All of Examples 1 to 1
Similar to No. 3, it showed a good value.

Example 7 As an aggregate, a passing value under a sieve of 0.15 mm was 4.7% by weight,
Example 2 except that spherical aggregate (NK grit manufactured by Nippon Kokan Co., Ltd.) having a residual value on the 2.5 mm sieve of 1.1% by weight was used.
And kneaded under the same conditions as above to obtain mortar. As shown in Table 1, by using the spherical aggregate, the mortar flow is remarkably increased and the strength of the material on the 1st day is slightly inferior,
A compressive strength of 900 kgf / cm ² or more was obtained after 3 days of material age.

Examples 8 and 9 Mortars having the same composition as in Example 2 were prepared except that the pressure in the mixer was 0.7 atm and 0.4 atm during the kneading. The mortar flow is slightly smaller,
Greatly enhances strength.

Example 10 As a hydration accelerator, kneading was carried out under the same conditions as in Example 2 except that 1.0 part by weight of calcium nitrite was added to the binder in addition to the ingredients of Example 2. , With mortar. Despite a large decrease in mortar flow over time, it exhibits extremely excellent rapid hardening properties, with 1200 kgf /
A compressive strength of cm ² or more was obtained.

Examples 11 to 16 and Comparative Examples 2 and 3 Example 2 was repeated except that a part of the Portland cement shown in Example 2 was replaced with the ultrafine powder shown in Table 2 as the binder.
And kneaded under the same conditions as above to obtain mortar. In each of the examples of the present invention, the mortar flow was increased, the workability was improved, and the short-term strength was increased. However, when the substitution amount of the ultrafine powder exceeded 20% by weight (Comparative Example 2), workable fluidity was not obtained, and ordinary cast molding was impossible. Further, as shown in Comparative Example 3, when the water / binder ratio was 25% by weight, mortar flow was obtained, but the compressive strength on the 3rd day was 700 k.
It was about gf / cm ² .

[0028]

[Table 2]

Comparative Examples 4 and 5 As a high-performance water reducing agent, a naphthalenesulfonic acid-based high-performance water reducing agent (Mighty 150 manufactured by Kao Corporation) was used.
Example 2 except that the binder ratio was 19 and 25% by weight
And kneaded under the same conditions as above to obtain mortar.

Comparative Examples 6 and 7 As an aggregate, a passing value under a sieve of 0.15 mm was 8.5% by weight,
Mortar was kneaded under the same conditions as in Example 2 except that natural Ogasayama sand having a residue value on the 2.5 mm sieve of 13.7% by weight was used and the water / binder ratio was 19 and 25% by weight. did.

Comparative Examples 8 to 11 Portland cement shown in Table 3 was used as a binder, and the water / binder ratio was changed to the value shown in Table 1 except that kneading was carried out under the same conditions as in Example 2 to prepare mortar. did.

[0032]

[Table 3]

In Comparative Examples 4 to 11, when the water / binder ratio was 20% by weight or less, no workable fluidity was obtained. Although a workable mortar flow was obtained only when the water / binder ratio exceeded 20% by weight, a high-strength cured product could not be obtained.

[0034]

As described above, according to the present invention,
The water / binder weight ratio of 0.20 or less and the fine aggregate / binder weight ratio of 0.20 or more are used under extremely severe conditions without using a special molding method such as pressure molding, and have good workability and sufficient workability. Working time can be secured, and a high-strength hydraulic cured product can be obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI technical display location C04B 14:02 Z 22:08) B 103: 30 (72) Inventor Shunichiro Uchida Sakura City, Chiba Prefecture 2-4-2 Daisaku Inside Central Research Laboratory, Onoda Cement Co., Ltd.

Claims (17)

[Claims] 1. A binder / aggregate, a polycarboxylic acid-based superplasticizer, and water, and a water / binder weight ratio of 0.10.
A hydraulic formulation, characterized in that it is ˜0.20. 2. The binder is a Portland cement having a hydraulic modulus of 2.20 or more, a Blaine specific surface area of 4000 cm ² / g or more and a 30 μm sieve residue value of 10 to 20% by weight. Item 2. A hydraulic composition according to item 1. 3. Portland cement 8 in which the binder has a hydraulic modulus of 2.20 or more, a Blaine specific surface area of 4000 cm ² / g or more, and a residue value on the 30 μm sieve of 10 to 20% by weight.
0 part by weight or more, and a Blaine specific surface area of 10000 cm ² /
2. The hydraulic composition according to claim 1, which comprises 20 parts by weight or less of ultra-fine powder of g or more. 4. An aggregate comprising fine aggregate whose particle size is adjusted so that 5% by weight or less of particles pass through a sieve of 0.15 mm, and a fine aggregate / binder weight ratio is 0.20 or more. The hydraulic compound according to any one of claims 1 to 3, which is characterized in that. 5. The hydraulic compound according to claim 4, wherein the fine aggregate has a particle size adjusted so that the residual value on the sieve of 2.0 mm is 5% by weight or less. 6. The hydraulic composition according to claim 4, wherein the fine aggregate is a spherical aggregate. 7. A hydration accelerator of 2.0 wt% or less is included with respect to 100 parts by weight of the binder.
~ The hydraulic composition according to any one of 6 to 6. 8. The hydraulic formulation according to claim 7, wherein the hydration accelerator is calcium nitrite. 9. A hydraulic compound containing a binder, an aggregate, a polycarboxylic acid-based high-performance water reducing agent, and water is kneaded at a water / binder weight ratio of 0.10 to 0.20 to form a mixture. A method for producing a hydraulically cured product, which comprises: 10. The method for producing a hydraulically cured product according to claim 9, wherein the mixture is kneaded at atmospheric pressure or less. 11. The binder is a Portland cement adjusted to have a hydraulic modulus of 2.20 or more, a Blaine specific surface area of 4000 cm ² / g or more, and a residue value on the 30 μm sieve of 10 to 20% by weight. Item 10. A method for producing a hydraulically cured product according to Item 9 or 10. 12. The Blaine ratio is 80% by weight or more of Portland cement adjusted to a binder having a hydraulic modulus of 2.20 or more, a Blaine specific surface area of 4000 cm ² / g or more and a 30 μm sieve residue value of 10 to 20% by weight. Surface area 10000 cm ²
The method for producing a hydraulically cured product according to claim 9 or 10, characterized by comprising 20 parts by weight or less of ultrafine powder of not less than / g. 13. An aggregate comprising fine aggregate whose particle size has been adjusted so that 5% by weight or less of particles pass through a sieve of 0.15 mm, and a fine aggregate / binder weight ratio is 0.20 or more. The method for producing a hydraulically cured product according to any one of claims 9 to 12, characterized in that. 14. The method for producing a hydraulically set product according to claim 13, wherein the fine aggregate has a particle size adjusted so that the residual value on the sieve of 2.0 mm is 5% by weight or less. 15. The method for producing a hydraulically cured product according to claim 13 or 14, wherein the fine aggregate is a spherical aggregate. 16. The hydraulic setting according to claim 9, wherein the hydraulic composition contains 2.0% by weight or less of a hydration accelerator with respect to 100 parts by weight of the binder. Body manufacturing method. 17. The method for producing a hydraulically cured product according to claim 16, wherein the hydration accelerator is calcium nitrite.