JPS6077159A - High strength cement composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a high-strength cement composition that hardens quickly and exhibits high strength. In the present invention, the high-strength cement composition includes not only ordinary concrete but also 4-stroke and mortar.

Conventionally, ordinary Portland cement has been widely used, but it takes a long time to finish setting, which is considered a major drawback in industrial production. For this reason, various proposals have been made to blend early-strengthening cement into ordinary Portland cement in order to promote its setting, but jet cement (
For example, according to a report by Onoda Cement Co., Ltd. and the Central Research Institute, mixing jet cement must be strictly controlled during jet cement production. It has been announced that the balance of the mineral composition values that were present in the steel is disrupted, resulting in abnormalities in coagulation and hardening. For this reason, it is prohibited to mix jet cement with ordinary Portland cement. Jet cement, which exhibits practical strength 2 to 3 hours after water injection, develops its strength due to ``ettringite'' produced by the water use reaction between C, □A7 Ca F2 and gypsum, and its strength increases after the first day of age. It is said that this occurs due to the hydration reaction of the aritto phase (C3S).In jet cement, the above two stages of water utilization reactions are carried out in a well-balanced manner, and each step is carried out at the manufacturing stage to ensure normal strength development. Mineral composition is strictly controlled.

However, when jet cement and ordinary portland cement are mixed, the semi-aqueous cement present in ordinary portland cement mixes into the jet cement, which abnormally delays the setting and hardening of the jet cement and increases its strength. In addition to poor expression, anhydrous gypsum is consumed by C3A, which normally exists in 8 to 10 units of Portland cement, and the balance of mineral composition values such as aluminate and ammonium gypsum, which were strictly controlled during jet cement production, is disrupted. As a result, abnormalities occur in the setting and hardening of the mixed cement. Furthermore, depending on the blending ratio of ordinary Portland cement and jet cement, the A degree may be lower than when ordinary Portland cement is used alone, and the advantage of jet cement's ultra-fast hardening properties is completely lost.

However, if a mortar mixed with ordinary Portland cement and jet cement is submerged in water immediately after it has finished setting, it will suffer from poor stability, such as cracks due to expansion tI and slight warping on the surface. I11. L
In the case of a mixed cement containing 75 parts by weight of ordinary Portland cement and 25 parts by weight of jet cement, there is a problem that the occurrence of cracks and sores changes depending on the temperature difference and the period of submergence, making it extremely unstable.

In view of the above circumstances, the present inventors investigated various blending compositions in order to improve the curing failure of mixed cement of ordinary Portland cement and jet cement, and to obtain a cement composition that hardens quickly and exhibits high strength. Among them, when one or more fine aggregates selected from α-quartz and its derivatives and halloysite and its derivatives are blended with a mixed cement of ordinary Portland cement and jet cement, ordinary Portland cement 50 When 10 to 20 parts by weight of the above-mentioned fine aggregate is mixed with 100 parts by weight of mixed cement of ~80 parts by weight and 50 to 20 parts by weight of jet cement, it sets quickly and does not cause poor hardening.
Furthermore, the present inventors have discovered that a high-strength cement composition that does not suffer from cracking or warping due to shrinkage during setting can be obtained, and that the above object can be effectively achieved, leading to the present invention.

The present invention will be explained in more detail below.

The high-strength cement composition according to the present invention contains ordinary tiltland cement, jet cement, and one or more fine aggregates selected from α-quartz, α-quartz derivatives, halloysite, and halloysite derivatives. This is what happens.

In this case, is the high strength cement composition of the present invention a normal column? Rutland cement 50-80 parts by weight, especially 60 parts by weight
-80 parts by weight of jet cement and 50 to 20 parts by weight, especially 40 to 20 parts by weight of the above-mentioned fine bone bone is blended with 5 to 30 parts by weight, especially 10 to 20 parts by weight, to 100 parts by weight of mixed cement. preferable.

Here, as the α-quartz, silica sand containing a large amount of α-quartz may be used. Further, the α-quartz derivative can be obtained by subjecting α-quartz and barium hydroxide to a hydrothermal reaction by boiling under normal pressure and refluxing reaction or by autoclave reaction under pressure (preferably at 6 atmospheres or less and 160°C or less). Keif
le barium (BaO.S i 02.H2O) can be suitably used. In addition, as the above-mentioned barium silicate, α-
B a per mole of quartz.

Particularly preferred is one obtained by hydrothermally reacting 0.2 mol or less of barium hydroxide.

Halloysite (A40g.2SiO2.4) (,0) Although both the anhydride of 7A and the hydrate of IOA can be used, it is more preferable to use the anhydride of 7λ.

In addition, as a halloysite derivative, halloysite and barium hydroxide are subjected to a boiling reflux reaction under normal pressure or an autoclave reaction under pressure (preferably at 6 atmospheres or less and 160°C or less).
Barium halloysite obtained by hydrothermal reaction (
Ba0-AL203.3SiO,.nH2O, however, n2-10) can be preferably used, but ordinary sodium A
There is no problem in using type zeolite etc. It is particularly preferable that the barirhamno-leusite is obtained by hydrothermally reacting 1 mol or less of barium hydroxide as BaO per 1 mol of halloysite.

In addition, in the present invention, fly ash or a derivative thereof can be used in combination with the above-mentioned fine aggregate, and a molded product having extremely superior heat resistance than K can be obtained.

The high-strength cement composition of the present invention is formed by mixing the above-mentioned components, but in the present invention, components such as a grouting agent, a rust preventive agent, a coloring agent, a waterproofing agent, and an organic polymer material are also added. You can mix them as appropriate.

As described above, the high-strength cement composition of the present invention contains one or more selected from α-stone pods, α-quartz derivatives, halloysite, and halloysite derivatives in a mixed cement of ordinary Portland cement and jet cement. By incorporating fine aggregate, it is semi-hard and exhibits high strength, and is less likely to crack or warp during solidification.

In this case, the high-strength cement composition of the present invention has a
It can be demolded within minutes, compared to the conventional Portland cement that takes about 2 days to demold, and the time required for demolding is significantly shortened.Productivity and economic efficiency are significantly improved. It is something that contributes.

Next, production examples of α-quartz derivatives and halloysite derivatives used as fine aggregates in the present invention will be shown.

[Production Example 1] α-quartz 1252 and Ba(α()2.8■b051) were placed in a 1 ton three-diameter round bottom flask, and 300 μm of water was poured into the flask. Using a reaction apparatus equipped with a cooling tube, a thermometer, an N2 gas inflow pipe, and a heating mantle heater, the above mixture is stirred and heated under normal pressure under N2 gas inflow, and further refluxed for 4 hours after the start of boiling, After that, let it cool naturally for about 60~70'
Cool with Ct and collect the reactant precipitate. The obtained reaction precipitate is thoroughly washed with about 500 ml of hot water at 70 to 80°C and heated again. After drying the reaction precipitate thus obtained in an electric dryer (set at 90°C) for more than 8 hours,
Leave to cool at room temperature, 122f BaO・5i02・J(2
I got 0. In addition, the reaction tear fluid that was filtered twice was
60me was collected and used as a final sample for neutralization titration.

[Production Example 2] α-quartz 1251 and 13a (OH)2. ” 8H2
018f was placed in a 1 ton three-diameter round bottom flask, and 300 me of water was poured into it. Thereafter, the same process as in Production Example 1 was carried out to obtain 1301 BaO8in2.H,O. Also, 9 old IV+-I ax filtrate s-1t
The solution was diluted to 10%, and 10% of the solution was collected and used as a final sample for neutralization titration.

[Production Example 3] α-quartz 1251 and Ba (α(), -8H, 036t
into a 1 ton three-diameter round bottom flask, and add 300 ml of water into the flask.
inject. After that, the same operation as in Production Example 1 was performed,
1311 of BaO-8iO7.N20 was obtained. Also, 2
Dilute the P liquid that has passed through the sea several times to 1 ton, and 1
0 was collected and used as a final sample for neutralization titration.

[Manufacturing Example 4] α-quartz 125f and Ba(OR)2@8'H208
Place 6 ml of water in a 1 ton three-diameter round bottom flask, and add 30 ml of water.
Inject 0go. Thereafter, the same operation as in Production Example 1 was performed to obtain 133 pieces of BaO-8iO2.N20. Also,
The filtrate obtained twice was diluted to 1 t, and 5% of the filtrate was collected and used as a sample for neutralization titration.

[Production Example 5] α-quartz 1252 and Ba(OFI)2-8H2012
Place 5 ml of water in a 1 ton three-pole round bottom flask, and add 30 ml of water.
0rn! , inject. The same 'i' as in Production Example 1
t production t row h v, 132 f tD BaO8i02
・HtO was obtained.

In addition, the filtrate that was filtered twice was diluted to 1 t, and 5. me was collected and used as a sample for neutralization titration.

In addition, using the samples for neutralization titration collected in Production Examples 1 to 5, the amount of Ba in the furnace liquid was determined by neutralization titration using an N/10 HC1 aqueous solution (power factor 1.004).

Here, the neutralization equivalent point in the middle 2o titration was determined by potentiometric titration. The results are shown in Table 1.

Table 1 [Production Example 6] Silica sand (α-8in2) 2 was placed in an autoclave with a capacity of 1 t.
Remove 40f and Ba (OH)z .8 HzO10W, and add 450 ml of water into it. After reacting for 30 minutes under stirring at 160°C and 5.5 atm, the reactant was allowed to cool while stirring until it reached about 60°C, and the reactant was taken out. Next, the reaction product is heated in a hot water bath, and while hot, the crystallized material is removed in a vacuum oven using a nutsche. This crystalline substance is dispersed in about 400 ml of ion-exchanged water, heated in a hot water bath (80°C), and the crystalline substance is collected under reduced pressure.

This crystalline substance was further washed with about 100°C of water, and then dried at 90°C in a dryer to form white crystals of BaO-8ift.
・HtO242,52 was obtained. In addition, the reaction r solution that had been filtered twice was diluted to 16%, and 60% of the diluted solution was collected and used as a sample for neutralization titration. (Hereinafter, Production Example 7
- 12). The analysis results of the silica sand used and the target material obtained by X-ray diffraction are shown in @Table 2 and Table 3.
Shown in the table. The apparatus and measurement conditions used for analysis are as follows.

Equipment: Xm generator manufactured by Rigaku Denki Co., Ltd. Goniometer 2155D for powder diffraction Measurement conditions X-rays Cu- to α (using Ni filter) tube voltage-
Tube current 35KV-15mA Slit system DSI.

R, S, 0.15m 5SI.

Detector S, C.

Table 2 20.90 4.250 70.00 2124.00
3.707 9.00 226.70 3.338
330.00 10031.00 2.884 2.0
0 036.60 2.455 47.00 1439
．． 50 2.281 41.00 1240.30 2
．． 237 22.00 642.50 2.126 3
5.00 1045.80 1.981 25.00
750.20 1.817 76.00 2354.9
0 1.672 25.00 755.30 1.66
1 9.00 257.20 1.610 2.00
060.00 1.541 50.00 1564.1
0 1.452 9.00 265.80 1.419
2.00 067.80 1.382 34.00
106B, 00 1.378 20.00 668.2
0 1.375 38.00 1168.40 1.3
71. 40.00 1273.50 1.288 1
0.00 375.70 1.256 16.00 4
77.70 1.22g 8.00 279.90 1
．． 200 15.00 42THETA(DEG,),
According to the results in Table 2, it was expected that the silica sand used contained a large amount of α-quartz.

Table 3 21.35 4.161 46.00 323.50
3.785 55.00 424.10 3.692
26.00 125.90 3.439 12.00
026.70 3.338 ＊＊＊＊＊ 10027.
80 3.208 14.00 128.10 3.1
75 14.00 133.90 2.644 8.0
0 036.55 2.458 145.00 103
9.50 2.281 130.00 940.30
2.237 60.00 442.50 2.126
105.00 745.90 1°977 85.00
650.10 1.820 492.00 3654
．． 95 1.670 66.00 455.40 1.
658 35.00 260.00 1.541 16
2.00 1264°10 1.452 32.00
265.80 1.419 10.00 067.80
1.382 104.00 768.20 1.37
5 169.00 1268.40 1.371 16
7.00 1273.50 1.288 39.00
275.70 1.256 54.00 477.80
1.227 25.00 12T)T11i1'l'
A(D]1ilX;, ), D(ANGSTROM) According to the results in Table 3, the chemical formula of the reactant is BaO-8i02.
It turned out to be H,O.

[Production Example 7] Contents (silica sand (α-8i02
)2502 and Ba(OH)! Remove -8H,020f and pour 400ml of water into it. Thereafter, this was treated in the same manner as in Production Example 6 to obtain BaO-8iOt"HtO26
I got 4g.

[Production Example 8] Contents - Silica sand (α-8ift
) 2502 and Ba(OH)t-sa,o 36t, and add 400% of water therein. Thereafter, this was treated in the same manner as in Production Example 6 to obtain BaO・5iOt”HtO2
Obtained 54t.

[Production Example 9] Silica sand (α-8iO□) 2 in an autoclave with contents tlt
50f and Ba (OH) * ・8 Remove 60t of HtO, and add 550ml of water therein. Thereafter, this was treated in the same manner as in Production Example 6 to form BaO-8iO1.H2O277.
I got f.

[Production Example 10] Silica sand (α-8iOy) 2 was placed in an autoclave with an internal capacity of 1 t.
Remove S02 and Ba(OH)t"8Hz072f, and add 400d of water into it. Then, treat this in the same manner as in Production Example 6 to obtain BaO・SiO2・H7O280f.
I got it.

[Production Example 11] Add 2 silica sand (α-8iOz) to an autoclave with a capacity of 1 t.
501 and Ba(OH)t @ sa, o 172 f
Then, pour 500ml of water into this. Thereafter, the filtrate was treated in the same manner as in Production Example 6 to form BaO・Stow・H2
O320f was obtained.

[Production Example 12] Silica sand (α-8in2
) 250 and Ba(OH)t @ 8H20250f
Then, pour 500ml of water into this. Thereafter, this was treated in the same manner as in Production Example 7 to obtain BaO・5ift”Ht
O299f was obtained.

Note that the samples for neutralization titration collected in Production Examples 6 to 12 were subjected to neutralization titration using an N/10 HC1 aqueous solution (power factor 1.004) (phenolphthalein indicator). Also,
The obtained target powder 0.11 was treated with hydrofluoric acid to volatilize and remove the silica content, then dissolved in dilute nitric acid, and this was used as a sample for IPC emission analysis using an SPS 1100 plasma emission spectrometer. Measuring Ba Hfl in a small powder,
The reaction rate of Ba was calculated from this and the blended Ban. The results are shown in Table 4.

In Table 4, ``chi'' indicates weight %.

Table 4 [Production Example 13] Halloysite 125f and Ba(OH)z ・8HzO
5y was placed in a 1 ton round bottom flask, and 3 ml of water was poured into it. Next, using a reaction apparatus A equipped with an electric stirrer, a Dimroth cooling tube, a thermometer, an N2 gas inflow tube, and a heating mantle heater, the above mixture was stirred and heated under normal pressure while flowing N2 gas, and was further boiled. Reflux for 3.5 minutes after starting, then let it cool naturally for about 60 minutes.
Cool to ~70°C and allow the reactants to precipitate. The resulting reaction precipitate is thoroughly washed with about 500° C. of hot water at 70 to 80° C. and filtered again. After drying the reaction precipitate thus obtained in an electric dryer (set at 90°C) for 8 hours or more,
The mixture was allowed to cool at room temperature to obtain barium halloysite with a temperature of 127.3F. In addition, 1 t of reaction F solution was filtered twice.
60% of the solution was diluted and used as a final sample for neutralization titration.

[Production Example 14] Halloysite 125v and Ba(OH)2.8 N20
Take 10 tons of water into three 1-ton round-bottomed flasks, and add 3 ounces of water into the flask.
Inject 00-. Thereafter, this was treated in the same manner as in Production Example 13, and 124. Of barium halloysite was obtained.

In addition, the filtrate that had been filtered twice was diluted to 1 t, and 60% of the filtrate was collected and used as a sample for neutralization titration.

[Production Example 15] Halloysite 125 and Ba(OH)z ・8 Ht
O181 was placed in a 1 ton round bottom flask, and 300 liters of water was poured into it. Thereafter, this was treated in the same manner as in Production Example 13 to obtain 126.3 F barium halloysite. In addition, the filtrate that had been filtered twice was diluted to 1 t, and 60 d of it was collected and used as a sample for neutralization titration.

[Production Example 16] Halloysite 125 and Ba (OH)z ・8H
Place zO361 in a 1 ton round bottom flask, and pour 300ml of water into it. Thereafter, this was treated in the same manner as in Production Example 13 to obtain 134.8 F barium halloysite. In addition, the F solution that had been filtered twice was diluted to 1 ton, and 60 liters of it were collected and used as a sample for neutralization titration.

[Production Example 17] Halloysite 3751 and Ba (OH)t ・8 N
20258 t% 2 t of three sets of round bottom flasks, and 900 ml of water is poured into the flasks. Thereafter, this was treated in the same manner as in Production Example 13 to obtain 410v Baliramno 10 Isite. In addition, in this case, 70 to 80 °C to wash the reaction precipitate.
lt hot water was used. In addition, the reactor liquid that had been filtered twice was diluted to 36%, and 5% of the diluted solution was collected and used as a sample for neutralization titration.

[Production Example 18] Halloysite 125v and Ba(OH)t'8H
Place LO 1251 into three 1 ton round bottom flasks and pour 300ml of water into them. After that, this was prepared in Production Example 13.
The same procedure as above was carried out to obtain 170.2 f Baliramno 10 isite. In addition, the reaction P solution that had been filtered twice was diluted to 1 t, and 5- of the diluted solution was collected and used as a sample for neutralization titration.

In addition, using the samples for neutralization titration collected in Production Examples 13 to 18, N/10 HCt aqueous solution (power factor 1.004)
The amount of Ba in the p solution was determined by neutralization titration using . In addition, the obtained target powder 0.12 was treated with hydrofluoric acid to volatilize and remove the silica content, then dissolved in dilute nitric acid, and this was used as a sample for IPC emission analysis using a 5PSI100 plasma emission spectrometer. The amount of Ba in the powder was measured, and the reaction rate of Ba was calculated from this and the amount of Ba blended. The results are shown in Table 5. In Table 5, ``chi'' is % by weight.

Next, examples will be shown to specifically illustrate the present invention.

〔Example〕

Production Examples 1 to 18 using fine aggregates with Ma of 1 to 25 shown in Table 6
It was manufactured in the same manner as. In this case, fine aggregate N(L
In Nos. 1 to 7 and j4α20 to 25, the raw material a and the raw material S were hydrothermally reacted by the same atmospheric pressure boiling reaction as in Production Example 1, and in the cases of fine aggregate N [18 to 19, the raw material a and the raw material S were Hydrothermal reaction was carried out by autoclave reaction under pressure similar to Production Example 6. In addition, the floors of manufacturing examples corresponding to fine aggregates Na 1 to 25 are also listed in Table 6.

Next, fine aggregate of N [L 1 to 25, α-5
Concrete molded products of Examples 1 to 32 having the compositions shown in Table 7 were manufactured using Ioz and halloysite, and their compressive strengths were measured. In this case, mechanical kneading was performed according to JIS standards (kneaded for 10 minutes with a dice mixer), 4
It was poured into a mold of X4X16 crn, and removed from the mold after about 30 minutes, immediately immersed in water, and then air-dried, and the compressive strength was measured on the 7th and 14th days.

The results are shown in Table 7. Note that Mighty 50 manufactured by Kako Soup Co., Ltd. was used as the water reducing agent. Further, in Table 7, A indicates the method of pulverizing the fine aggregate using a mortar, and B indicates the method of pulverizing the fine aggregate using a ball mill. Furthermore, in Table 7, the numbers in parentheses after fine aggregate N (L) indicate 111 of the corresponding manufacturing example.

According to the results in Table 7, the high-strength cement composition of the present invention was found to be semi-hard and exhibit high strength.

Furthermore, in Examples 1 and 2, Ba(OH)t・
When 8H10 was mixed with two cements and the compressive strength was measured on the 7th day after immersion in water, they were 10,700 and 11,600, respectively, indicating that the strength had clearly decreased.

In other words, sodium hydroxide has traditionally been added to cement to improve its strength, but barium hydroxide itself does not have this effect, and barium hydroxide is mixed with α-quartz or halloysite. It was found that only the reactants that were reacted improved the strength of cement.

Furthermore, according to the results in Table 7, the compressive strength of fine aggregates crushed in a mortar and sol mill was almost the same, and these fine aggregates showed approximately the same compressive strength. It was found that sufficient effects were obtained even when crushed in a mortar.

Applicant: Sekisui House Co., Ltd.

Claims (1)

[Claims] 1. Contains ordinary Portland cement, jet cement, and one or more fine aggregates selected from α-quartz, α-quartz derivatives, halloysite, and halloysite derivatives. A high-strength cement composition characterized by: 2. Cemented O mixed with 50 to 80 parts by weight of ordinary Portland cement and 50 to 20 parts by weight of jet cement.
Claim 1, wherein 5 to 30 parts by weight of one or more fine aggregates selected from α-quartz, α-quartz derivatives, halloysite, and halloysite derivatives are blended with respect to parts by weight of O. Strength cement composition. 3 α-quartz derivative causes α-quartz and barium hydroxide to undergo a hydrothermal reaction. Barium silicate (B
The high-strength cement composition according to claim 1 or 2, which is aO-3iOt.H,O). 4. The halloysite derivative is barium halloysite (BaO・A40.・38102・nH) obtained by hydrothermally reacting halloysite and barium hydroxide.
=o, where n=2 to 10).
The high-strength cement composition according to item 1 or 2.