JPH0748156A - Setting controlling agent of cement-based material and controlling method - Google Patents

Abstract

PURPOSE:To provide technology capable of freely controlling a time for setting of cement paste, cement mortar, concrete, etc. CONSTITUTION:This agent is the agent useful for controlling setting of cement- based materials and consists of a setting retarder and a setting initiator. The setting initiator is a substance for supplying a metal ion selected from the group consisting of Li<+>, Mg<2+>, Mn<2+>, Ba<2+>, Al<3+>, Fe<3+>, Ti<4+> and Sn<4+> and the setting retarder is a substance selected from an oxycarboxylic acid or its salt, an aminocarboxylic acid or its salt, a saccharide, a zinc compound, a silicofluoride and boric acid or its salt to give the objective setting controlling agent of cement-based material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a setting control agent and control method for cementitious materials.

[0002]

BACKGROUND OF THE INVENTION As one of the next-generation concrete technologies, "free control of setting / hardening (also simply referred to as setting) time" has been proposed. By the way, at present, accelerators, retarders and ultra-retarders are known as techniques for controlling the setting time, but these are only to accelerate the setting or to extend the setting earlier. However, the delay time is only determined by the performance and the amount added, and it is not possible to freely change the delay time.

[0003]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a technique capable of freely controlling the time for setting cement paste, cement mortar, concrete or the like. The object of the present invention is an agent used for controlling the setting of a cement-based material, which comprises a setting retarder and a setting initiator, and the setting initiator is Li ⁺ , Mg ²⁺ , Mn ²⁺ , Ba ^{2 +} , A
It is achieved by a setting control agent for cementitious materials, which is a substance which provides a metal ion selected from the group consisting of l ³⁺ , Fe ³⁺ , Ti ⁴⁺ and Sn ⁴⁺ .

Also, it is a method for controlling the setting of cement-based materials.
When a setting retarder is added to the cement-based material,
After the time is delayed compared to the time without addition, Li⁺, Mg²⁺，
Mn ²⁺, Ba²⁺, Al³⁺, Fe³⁺, Ti⁴⁺And Sn⁴⁺of
Add a substance that provides a metal ion selected from the group
According to the method for controlling the setting of cement-based materials,
Will be achieved.

Further, it is a method for controlling the setting of cement-based materials.
When a setting retarder is added to the cement-based material,
After the time is delayed compared to the time without addition, Li⁺, Mg²⁺，
Mn ²⁺, Ba²⁺, Al³⁺, Fe³⁺, Ti⁴⁺And Sn⁴⁺of
Condensation by a substance that provides a metal ion selected from the group
Predict the release of delay and add the specified amount of the substance at the specified time
According to the method for controlling the setting of cement-based materials,
Will be achieved.

In the above invention, the substance which provides a metal ion as a coagulation initiator may be an inorganic acid salt such as nitrate, sulfate or chloride, and glycolic acid or lactic acid as a coagulation retarder. , Oxycarboxylic acids such as hydroacrylic acid, α-oxybutyric acid, glyceric acid, malic acid, citric acid and tartaric acid, salts of these acids,
Aminocarboxylic acids, salts thereof, sugars such as sucrose, zinc compounds such as zinc oxide, silicofluorides such as magnesium silicofluoride and sodium silicofluoride, boric acid and borate can be used.

The present invention will be described in detail below. It is said that the initiation of the setting of cement is closely related to the change in the concentration of Ca ^{2+ in} the liquid phase and depends on the time when the concentration reaches a peak. That is, if there is a factor that shortens the time for which the degree of supersaturation becomes maximum, coagulation is promoted, and conversely, if there is a factor that prolongs it, it is delayed. Therefore, the retarder, or to suppress the dissolution of Ca ²⁺ into the liquid phase, the liquid phase Ca ²⁺
Those that reduce the ionic strength are equivalent. These include silicofluoride, phosphoric acid, salts thereof, boric acid, salts thereof, etc. which form a sparingly soluble calcium salt film layer on cement particles, oxycarboxylic acids complexing Ca ^2+, and salts thereof. , Aminocarboxylic acids, salts thereof, sugars and metal oxides.

The delaying agent may be added by dissolving it in water or simultaneously adding water to cement (simultaneous addition), and adding it after kneading cement and water in advance (post-addition). There is. Incidentally, simultaneous addition may cause abnormal stiffness or momentary setting, or a large amount of addition may be required to obtain a predetermined delay time, whereas post-addition avoids these phenomena. In addition, a larger delay effect is often obtained.

Considering the initiation of setting in a system in which such a retarder is used and the setting is delayed, it is conceivable that the cause of the delay should be stopped (released). Therefore, first, when the oxycarboxylic acid complexing Ca ²⁺ , its salt, aminocarboxylic acid, its salt, saccharides, metal oxides, etc. were used, as a result of conducting research, a calcium complex salt was formed. However, it was revealed that cement with delayed setting could start to set by eliminating its complex salt. Therefore, studies were conducted on a method of adding a metal ion that forms a complex salt that is more stable than calcium and complexing it with a retarder to eliminate the calcium complex salt and start the setting.

First, as a first experiment, the stability constant, which is a measure of the ease of complex formation, was examined. The stability constant of the citric acid complex is Al ³⁺ > Cu ²⁺ > Fe ²⁺ > Z
The order is n ²⁺ > Ca ²⁺ > Ba ²⁺ , and a metal salt that provides Al ³⁺ , Cu ²⁺ , Fe ²⁺ , Zn ^2+, etc., which has a stability constant larger than that of Ca ²⁺ , is added. It was considered good. However, this technical idea was not sufficient, that is, although successful in the case of Al ³⁺ , Cu ²⁺ , F
In the case of e ²⁺ and Zn ²⁺ , favorable results were not obtained.

Therefore, the idea of the stability constant, which is a measure of the ease of complex formation, is abandoned, and various metal salts are added to the delayed system using citric acid, which is a typical calcium complexing agent. However, when a good initiator was selected, Li ⁺ ,
Mg ²⁺ , Mn ²⁺ , Ba ²⁺ , Al ³⁺ , Fe ³⁺ , Ti ⁴⁺ , S
It was found that when a metal ion such as n ⁴⁺ was added, the calcium complex salt disappeared and coagulation started.

As a result of further research on these metal salts, it was found that coagulation also started in a system in which another type of retarder was used. This is understood for similar reasons when the retarder is complex-forming. On the other hand, although it was difficult to understand that the same effect was exerted on a system delayed by a poorly soluble salt-forming type such as sodium silicofluoride, magnesium silicofluoride or boric acid, this was as follows. it was thought. That is, it was considered that the elution of Ca ²⁺ , which was hindered by the poorly soluble salt film, was activated by the addition of the initiator and promoted hydration.

Li ⁺ , Mg ²⁺ , Mn ²⁺ , Ba ²⁺ , A
As a substance providing a metal ion selected from the group consisting of l ³⁺ , Fe ³⁺ , Ti ⁴⁺ and Sn ⁴⁺ , a salt of an inorganic acid such as nitrate, sulfate or chloride is generally used. C
Considering that l ⁻ is one of the causes of corrosion of reinforcing steel, it is more preferable that it is in the form of nitrate or sulfate.

The present invention will be described below with reference to specific examples.

[0015]

【Example】

[Example 1] As the cement, ordinary Portland cement manufactured by Chichibu Cement Co., Ltd. was used. The chemical components of the used ordinary Portland cement are shown in [Table 1], and the physical properties are shown in [Table 2].

Table 1 [Chemical composition (%)] ig.loss insol. SiO ₂ Al ₂ O ₃ Fe ₂ O ₃ CaO MgO SO ₃ N-1 1.3 0.1 21.6 5.2 2.8 64.4 1.7 2.0 N-2 1.3 0.1 21.8 5.2 2.8 64.2 1.6 2.0 N-3 1.3 0.1 21.4 5.3 2.8 64.4 1.7 2.0 Table 2 Specific gravity Specific surface area Condensation Mortar compressive strength (cm ² / g) Water content (%) Initial (hm) Final (hm) 3 days 7 days 28 days N -1 3.16 3230 27.7 2-35 3-40 153 265 422 N-2 3.16 3300 27.9 2-20 3-25 149 254 424 N-3 3.16 3310 27.9 2-25 3-30 152 250 418 * Starting and closing columns (Hm) in, for example, 2-35 means 2 hours and 35 minutes * The unit of mortar compressive strength is kgf / cm ² and the compounds shown in [Table 3] were used as retarders.

Table 3 Insoluble salt forming type magnesium silicate fluoride MgSiF ₆ · 6H ₂ O sodium silicate fluoride Na ₂ SiF ₆ boric acid H ₃ BO ₃ complex salt forming type citrate C ₆ H ₈ O ₇ sodium citrate Na ₃ C ₆ H ₅ O ₇・ 2H ₂ O Tartrate C ₄ H ₆ O ₆ Sodium tartrate Na ₂ C ₄ H ₄ O ₆・ 2H ₂ O Gluconic acid C ₆ H ₁₂ O ₇ Sucrose C ₁₂ H ₂₂ O ₁₁ Zinc oxide ZnO Above JIS is mixed under the condition of water content of 30%, JIS
A setting test according to R 5201 "Physical test method for cement" was performed. Tap water was used as the kneading water.
As the method for adding the retarder, both simultaneous addition and post-addition were adopted. Each retarder addition method is shown below.

[Simultaneous Addition] The retarder was dissolved in the kneading water in advance and added. However, zinc oxide, which has low solubility in water, was added to cement at the same time as water was added as powder. [Post-addition] First, add only cement and water according to JIS 3
The mixture was kneaded for a minute to form a paste, and then scraped off and added with a retarder in 1 minute, and subsequently kneaded again for 3 minutes in accordance with JIS. The retarder was added as a powder, and large crystalline particles such as citric acid and sucrose were crushed and added in an agate mortar.

Further, the cement paste obtained as described above was subjected to an abnormal setting test according to JASS5T-101 "Criteria for judging abnormal setting of cement".
Results of abnormal coagulation and coagulation test without addition of retarder [Table 4]
In addition, a retarder (citric acid, sucrose (citric acid, sucrose is N
-2 cement), and sodium silicofluoride and magnesium silicofluoride (sodium silicofluoride and magnesium silicofluoride are relative to N-3 cement)) are simultaneously added [Table 5 ], Retarder (citric acid, sucrose, magnesium silicofluoride, zinc oxide, boric acid (citric acid, sucrose, magnesium silicofluoride, zinc oxide and boric acid to N-1 cement), silicofluorine The results of post-addition of sodium bromide (sodium silicofluoride with respect to N-3 cement) are shown in [Table 6], and retarders (sodium citrate, tartaric acid, sodium tartrate, sodium gluconate (citric acid Sodium, tartaric acid, sodium tartarate and sodium gluconate against N-2 cement), gluconic acid (gluconic acid is N-3)
[Table 7] shows the results when)) was post-added to the cement. In addition, in [Table 5] to [Table 7], the added amount of the compound as the retarder is% by weight with respect to the cement.

Table 4 Abnormal coagulation (mm) Coagulation time 5 minutes later 10 minutes later First departure (hour-minute) Final termination (hour-minute) N-1 40 40 2-55 3-55 N-2 38 38 3-00 4-05 N-3 38 38 3-10 4-25 Table 5 Amount of citric acid added Abnormal condensation (mm) Condensation time 5 minutes after 10 minutes First departure (hour-minute) Termination (hour- Min) 0 38 38 38 3-00 4-05 0.100% 29 12 6-00 12-20 0.200% 39 36 0-35 1-35 0.500% 36 35 2-00 9-40 0.600 % 40 38 1-10-10 2-00 0.625% 40 38 1-50 8-50 0.675% 39 38 2-30 10-00 0.700% ^* 39 37 16-10 27-10 1.000% ^* 37 35 21-50 32-20 1.500% 37 35 30-10 52-10 2.000% 35 34 36-00 58-20 Amount of sucrose Abnormal setting (mm) Setting time 5 minutes 10 minutes After start (hour-minute) End (hour-minute) 0 38 38 3-00 4-05 0.050% 36 33 6-40 8-40 0.075% ^* 33 32 12-40 15-10 0.100% 38 38 35 19-20 22-10 0.110% ^* 36 33 25-10 27-40 0.125% 34 32 34-20 20 39-40 1.000% 0 0 1-20 3-10 Na Fluorosilicate Unusual Condensation (mm) Condensation Time Lithium Addition 5 min After 10 minutes First departure (hour-minute) Termination (hour-minute) 0 38 38 38 3-10 4-25 0.050% 40 38 38 5-00 7-00 0.100% 40 39 6-30 8-00 0 200% 39 38 7-40 9-30 0.300 % 39 38 9-40 11-20 0.400% ^* 40 39 10-20 12-30 0.500% 38 38 10-20 11-40 0.600% 38 37 9-40 12-00 0.800% 35 32 8-00 10-50 1.000% 32 27 8-8-10 11-00 2.000% 3 0 1-00 2-50 Fluoromagnesium fluoride Abnormal condensation (mm) Aggregation time 5 minutes later 10 minutes later First departure (hour-minute) Termination (hour-minute) 0 38 38 3-10 4-25 1.000% 37 35 35 8-10 11-20 1.500% 33 27 10-40 14- 00 2.000% ^* 32 31 12-10 16-30 3.000% 29 28 6-10 13-10 * in Table 5 indicates the addition amount at which the initial departure is around 12 hours and 24 hours. Table 6 Amount of citric acid added Abnormality Condensation (mm) Condensation time 5 minutes later 10 minutes later First (hour-minute) Termination (hour-minute) 0 40 40 2-55 3-55 0.075% ^* 40 40 11-15 13-45 0.100% 39 39 16-40 19-45 0.125% ^* 40 40 21-45 24-50 0.150% 40 40 28-40 32-30 Sucrose addition amount Abnormal coagulation Setting (mm) Setting time 5 minutes later 10 minutes after Start (hour-minute) End (hour-minute) 0 40 40 2-55 3-55 0.050% ^* 40 40 11-55 13-55 0. 075% 40 39 18-10 20-30 0.100% ^* 40 39 25-25 30-35 Fluoromagnesium Fluorofluorescean Coagulation (mm) Condensation time Cadmium addition amount 5 minutes after 10 minutes First start (hour -Min) Termination (hour-min) 0 40 40 2-55 3-55 0. 200% 40 40 6-45 8-15 0.500% 40 40 7-10 9-10 1.000% 39 38 9-45 11-05 1.500% 38 37 10-25 12-40 2.000% ^* 37 34 11-25 13-30 3.000% 26 27 8-8 25 12-25 Amount of added zinc oxide Abnormal condensation (mm) Condensation time 5 minutes 10 minutes later Start (hour-minute) Termination ( Hour-minute) 0 40 40 2-55 3-55 0.100% ^* 40 40 11-20 12-35 0.125% 40 40 16-05 17-25 0.150% 40 40 21-55 23-10 0.175% ^* 40 40 25-50 28-05 0.200% 39 40 28-10 29-40 boric acid addition amount unusual coagulation (mm) coagulation time 5 minutes after 10 minutes initial start (hour- Minute) End (hour-minute) 0 40 0 2-55 3-55 0.250% 40 40 8-50 10-20 0.300% 40 40 10-45 13-00 0.325% ^* 40 40 11-40 14-50 0.350% 40 40 13-00 15-55 0.450% ^* 40 40 24-24-00 28-55 Natrifluorosilicate Abnormal condensation (mm) Condensation time 5 minutes after the addition of lithium 10 minutes First (hour-minute) Termination (Hour-minute) 0 38 38 3-10 4-25 0.025% 40 40 7-50 10-20 0.050% 39 40 10-00 12-00 0.075% 40 40 10-50 12-30 0.100% 39 40 11-00 12-20 0.300% 40 40 11-20 13-20 0.400% ^* 40 40 10-50 13-10 0.500% 40 40 10-50 12-40 0 .600% 40 39 10-00 12-50 0.800% 39 37 8-20 10-50 1.000% 34 3 7-10 9-10 2.000% 3 2 Within 50-50 1-30 Table 6 The symbol * in the figure indicates the amount added at which the first train is around 12 hours and 24 hours. Table 7 Nato Citrate Abnormal Condensation (mm) Condensation time Amount of added lithium 5 minutes 10 minutes later First (hour-minute) Termination (hour-minute) 0 38 38 3-00 4-05 0.100% ^* 39 39 10-20 12-40 0.175% ^* 40 40 21-45 25-20 0.200% 40 40 28-35 31-00 Tartaric acid addition amount Abnormal setting (mm) Setting time 5 minutes 10 minutes later First departure (hour-minute) Termination (hour-minute) 0 38 38 38 3-00 4-05 0.100% 38 38 5-00 6-40 0.200% ^* 39 39 11-35 14-25 0.250% 40 39 18-50 20-40 0.275% ^* 39 39 21-30 23-50 Natri tartrate Abnormal coagulation (mm) Condensation time Amount of um added 5 minutes after 10 minutes First time (hour -Min) Termination (hour-min) 0 38 38 3-00 4-05 .100% 40 38 8-00 9-50 0.175% ^* 39 39 21-10 22-00 0.200% 40 39 28-50 30-00 gluconate isocyanatomethyl abnormal coagulation sintering (mm) between the time of condensation to Amount of added lithium 5 minutes later 10 minutes later First (hour-minute) Final (hour-minute) 0 38 38 3-00 4-05 0.050% ^* 40 39 10-50 13-10 0.075% ^* 40 40 24-30 26-50 0.100% 40 39 43-50 45-00 or more Gluconic acid Abnormal coagulation (mm) Condensation time Addition amount 5 minutes 10 minutes later Start (hour-minute) Termination (hour-) Min) 0 38 38 3-10 4-25 0.075% 40 40 8-50 11-00 0.100% ^* 40 40 13-30 16-50 0.125% ^* 40 40 20-40 24-10 Table * In 7 starts for 12 hours and Indicating the amount to be around 4 hours. According to this, addition of oxycarboxylic acids such as citric acid and its salts, sugars such as sucrose, silicofluorides such as sodium silicofluoride and magnesium silicofluoride, zinc compounds such as zinc oxide, and boric acid causes coagulation. You can see that it can be delayed. Depending on the type and amount of drug added, the onset of coagulation can be delayed for more than 24 hours. Therefore, it is understood that by appropriately selecting the type and addition amount of the retarder, the initiation of setting of the cement paste can be sufficiently extended to the time practically required for controlling the setting.

Further, when comparing the amounts of the retarder added so that the starting time is around 12 hours and 24 hours between the simultaneous addition and the post-addition, particularly in the case of citric acid, the post-addition requires a smaller addition amount, It can be seen that a large delay effect can be obtained. Next, with respect to the cement paste in which the setting was delayed as described above, the compounds shown in the following [Table 8] were added to try to start the setting.

Table 8 Mg compound Magnesium nitrate Mg (NO ₃ ) ₂ · 6H ₂ O Al compound Aluminum chloride AlCl ₃ · 6H ₂ O Aluminum nitrate Al (NO ₃ ) ₃ · 9H ₂ O Aluminum sulfate Al ₂ (SO ₄ ) ₃ · 14~18H ₂ O aluminum oxide Al ₂ O ₃ Fe compounds iron _{(II) FeCl 2 · nH 2} O iron chloride _{(III) FeCl 3 · 6H 2} O nitrate iron chloride _{(III) Fe (NO 3)} 3 · 9H 2 O iron sulfate _{(II) FeSO 4 · 7H 2} O iron sulfate _{(III) Fe 2 (SO 4} ) 3 · nH 2 O triiron tetroxide Fe ₃ O ₄ iron sesquioxide Fe ₂ O ₃ Cu compounds copper chloride CuCl ₂ · 2H ₂ O Copper nitrate Cu (NO ₃ ) ₂・ 3H ₂ O Copper sulfate CuSO ₄・ 5H ₂ O Ba compound Barium chloride BaCl ₂ Zn compound Zinc chloride ZnCl ₂ Pb compound Lead chloride PbCl ₂ Lead nitrate Pb (NO ₃ ) ₂ ( In the following description, compound water is omitted.) For example, cement pace with a starting time of about 20 hours by post-adding 0.125% citric acid as a retarder Becomes systems from various metal salts initiator _{(Mg (NO 3) 2,} AlCl 3,
Al ₂ O ₃ , Al (NO ₃ ) ₃ , Al ₂ (SO ₄ ) ₃ , FeCl ₂ , FeCl ₃ , Fe ₃ O
₄ , Fe ₂ O ₃ , Fe (NO ₃ ) ₃ , FeSO ₄ , Fe ₂ (SO ₄ ) ₃ , CuCl ₂ ,
Cu (NO ₃ ) ₂ and CuSO ₄ are added to the cement system of N-2, and BaCl ₂ , ZnCl ₂ , PbCl ₂ and Pb (NO ₃ ) ₂ are N-.
[Table 9] shows the setting time when (added to the cement system of 3) was added 6 hours after contact with water. In addition, in [Table 9], the addition amount of the compound as the initiator is shown by weight% with respect to the cement. In addition, the setting time in the tables after [Table 9] is the time from the addition of the initiator when the initiator was added, and the time from the contact with water when the initiator was not added.

Table 9 Initiator Addition Amount Coagulation Time Evaluation Start / End (hour-minute) (hour-minute) No addition 20-15 23-00 Mg (NO ₃ ) ₂ 1.0% 4-10 5-10 ○ Mg (NO ₃ ) ₂ 2.0% 3-00 3-40 ◎ AlCl ₃ 0.5% 7-50 10-40 △ AlCl ₃ 1.0% 4-20 5-20 ○ AlCl ₃ 2.0% 6-50 8-10 △ Al ₂ O ₃ 2.0% 11-50 14-40 × Al ₂ O ₃ 5.0% 11-40 14-50 × Al (NO ₃ ) ₃ 2.0% 8-10 9-40 △ Al (NO ₃ ) ₃ 3.0% 6-508 -00 ○ Al ₂ (SO ₄ ) ₃ 1.0% 7-30 9-10 △ Al ₂ (SO ₄ ) ₃ 2.0% 4-20 4-40 ◎ Al ₂ (SO ₄ ) ₃ 3.0% Within 1-00 1- 50 ◎ FeCl ₂ 1.0% 13-50 15-50 × FeCl ₂ 2.0% 9-20 11-30 △ FeCl ₃ 1.0% 5-30 6-40 ○ FeCl ₃ 2.0% 2-40 3-20 ◎ FeCl ₃ 3.0% 2-10 2-30 ◎ Fe ₂ O ₃ 2.0% 10-50 13-30 △ Fe ₂ O ₃ 5.0% 11-10 13-40 △ Fe ₃ O ₄ 2.0% 12-10 14-20 × Fe ₃ O ₄ 5.0% 11-40 13-50 △ Fe (NO ₃ ) ₃ 0.5% 5-00 7- 20 ○ Fe (NO ₃ ) ₃ 1.0% 4-00 5-30 ○ Fe (NO ₃ ) ₃ 2.0% 4-40 5-50 ○ FeSO ₄ 2.0% 24-00 26-20 × Fe ₂ (SO ₄ ) ₃ 2.0% 5-30 6-50 ○ Fe ₂ (SO ₄ ) ₃ 3.0% 3-50 5-20 ○ CuCl ₂ 2.0% Curing failure × Cu (NO ₃ ) ₂ 2.0% Curing failure × CuSO ₄ 2.0% Curing failure × * Above is for N-2 cement * Below is no addition for N-3 cement 20-35 23-05 BaCl ₂ 1.0% 9-20 11-30 △ BaCl ₂ 2.0% 4-00 5- 20 ○ ZnCl ₂ 2.0% 7-40 9-30 △ PbCl ₂ 2.0% 18-10 21-00 × Pb (NO ₃ ) ₂ 2.0% 24 hours or more × As the effect of the initiator, the setting time after the initiator is added Is when no retarder is added (when the amount of water is 30%, ; About 3 hours, the termination;
It is desirable that it becomes almost the same as about 4 hours). Therefore,
The effect of the initiator was divided into four grades, the termination of which was within 5 hours, within 8 hours, within 14 hours and over 14 hours after the addition of the initiator, and ⊚, ◯, Δ, and × were shown in the table, respectively.

When magnesium nitrate is added, a starting effect is recognized, and particularly when 2.0% is added, the setting time from the addition of magnesium nitrate is the same as when no retarder is added, showing an excellent setting start effect. With Als, the setting time does not change significantly when aluminum oxide is added, but it becomes shorter when aluminum chloride, aluminum nitrate, or aluminum sulfate is added. In particular, aluminum sulphate shows a marked starting action.

[0025] In Fe compounds, addition of iron sulfate (Fe ^2+), but becomes the condensation is further delayed, iron nitrate (Fe ^3+), iron sulfate (Fe ^3+), iron chloride (Fe ³⁺ ) Is added, the effect of initiating setting is recognized. It can be seen that addition of Cu causes poor curing. The effect of initiating condensation is recognized by the addition of barium chloride.

[Table 10] When Mg (NO ₃ ) ₂ , AlCl ₃ , FeCl ₃ , Fe (NO ₃ ) ₃ which had been added after 6 hours of contact with water and had an initiation action were added after 3 hours of contact with water The result is shown. Table 10 Amount of initiator added 3 hours after contact with water 6 hours after contact with water Condensation time (hour-minute) of addition after contact with water (hour-minute) Start-stop Start-stop Mg (NO ₃ ) ₂ 2.0% 3-00 3-50 3-00 3-40 AlCl ₃ 1.0% 4-50 5-40 4-20 5-20 FeCl ₃ 2.0% 2-40 3-20 2-40 3-20 FeCl ₃ 3.0% 2-10 2-30 2-10 2-30 Fe (NO ₃ ) ₃ 1.0% 3-40 5-50 4-0 5-30 Fe (NO ₃ ) ₃ 2.0% 4-30 5-50 4-40 5 The -50 * setting time is from the initiator addition. That is, a comparison with the result of addition after 6 hours of contact with water was shown, which shows that almost the same starting action is exhibited.

Tables 11a to 11d show the results when the initiator was added to a system in which various retarders were post-added and the initial delay was delayed to around 12 hours or 24 hours. Table 11a Initiator addition amount Setting time (hour-minute) Starting and ending Fe (NO ₃ ) ₃₀ % (no addition) 23-45 27-45 0.5% 5-10 10-20 1.0% 2-20 6-40 * Sucrose is the retarder, the added amount is 0.100%, and the starting point is about 24 hours. Iron nitrate (Fe (NO ₃ ) ₃ ) is added 6 hours after the contact with water, cement cement of N-2. Table 11b Initiator addition amount Setting time (hour-minute) Starting and ending AlCl ₃ 0% (no addition) 22-10 25-30 1.0% 4-10 5-30 * Boric acid is the retarder. , The added amount is 0.450%, starting time is about 24 hours Aluminum chloride is added 6 hours after contact with water, N-3 cement type is used Table 11c Initiator addition amount Setting time (hour-minute) beginning onset end forming _{Fe (NO 3) 3 0%} ( no addition) 11-00 12-20 1.0% 4-30 5-50 * retarder sodium silicofluoride fluoride , The amount added is 0.1
It is 00%, the first train is about 12 hours, iron nitrate (Fe (N
O ₃ ) ₃ ) is added 1 hour after contact with water and N-3 cement type is used. Table 11d Initiator addition amount Setting time (hour-minute) Starting and ending Fe (NO ₃ ) ₃ 0% (None Addition) 10-45 13-50 1.0% 5-00 7-20 * Magnesium silicofluoride is the retarder, and the addition amount is 2.
000%, the first train is about 12 hours, iron nitrate (Fe (N
O ₃ ) ₃ ) is added after 1 hour of contact with water, and the cement system of N-3 is used. According to this, the effect of the initiator is similarly obtained even when the retarder is not a citric acid-based saccharide, boric acid or fluorosilicate. You can see that is being played.

Further, in [Table 12a to Table 12d], various oxycarboxylic acid type retarders were post-added to the system in which the initial delay was delayed to about 24 hours, and the initiator was added 6 hours after the contact with water. The results are shown. Table 12a Initiator addition amount Setting time (hour-minute) Starting and ending AlCl ₃ 0% (no addition) 20-15 23-00 1.0% 4-20 5-20 2.0% 6-50 8-10 Fe (NO ₃ ) ₃ 1.0% 4-00 5-30 2.0% 4-40 5-50 * The retarder is citric acid, the amount added is 0.125%, and the starting point is about 24 hours N-2 cement type Table 12b Initiator addition amount Setting time (hour-minute) Starting and ending AlCl ₃ 0% (no addition) 22-05 25-50 1.0% 7-00 8-40 2.0% 6-00 7- 20 Fe (NO ₃ ) ₃ 1.0% 5-40 7-40 * The retarder is sodium citrate, and the addition amount is 0.1
75%, starting time is about 24 hours, N-3 cement type is used Table 12c Initiator addition amount Setting time (hour-minute) Starting and ending AlCl ₃ 0% (no addition) 21-25 22 -20 1.0% 7-00 8-00 2.0% 3-40 4-30 Fe (NO ₃ ) ₃ 1.0% 6-20 8-10 2.0% 3-10 5-30 * Addition of the retarder is sodium tartrate The amount is 0.17
5%, starting time is about 24 hours, N-3 cement type is used. Table 12d Initiator addition amount Setting time (hour-minute) Starting and ending AlCl ₃ 0% (no addition) 24-05 26 -10 2.0% 2-10 3-10 Fe (NO 3) 3 with 1.0% 5-20 6-50 * retarder sodium gluconate, the amount of addition is 0.
It is 075%, the starting time is about 24 hours, and the cement system of N-3 is used. According to this, it can be seen that the initiator effect of aluminum chloride or iron nitrate (Fe ³⁺ ) is exhibited.

In Tables 13a and 13b, aluminum chloride or iron nitrate was added to a system in which an amount of citric acid with an initial amount of about 24 hours and an amount of sodium silicofluoride with an initial amount of about 12 hours were simultaneously added. The setting time when (Fe ³⁺ ) is added is shown. Table 13a initiator amount coagulation between when forming (time - min) started onset final sintering AlCl ₃ 0% (no addition) 21-50 32-20 1.0% 6-40 22-20 1.5% 2-50 12-10 2.0 % 1-30 4-30 4.0% Instantaneous Fe (NO ₃ ) ₃ 2.0% 3-30 14-10 3.0% 4-30 7-20 4.0% 2-00 3-10 5.0% Within 1-00 1-50 * The retarder is citric acid, the amount of which is 1.000%, the starting point is about 24 hours. Aluminum chloride and iron nitrate (Fe (NO ₃ ) ₃ ) are added after 6 hours of contact with water. Usage table 13b Initiator addition amount Setting time (hour-minute) Starting and ending Fe (NO ₃ ) ₃₀ % (no addition) 10-20 12-30 1.0% 5-00 7-30 2.0% 4- 30 7-20 4.0% 2-30 3-00 * The retarder is sodium fluorosilicate, the addition amount is 0.40
0%, starting time about 12 hours, iron nitrate (Fe (NO ₃ ) ₃ )
Is added after 1 hour of contact with water. A cement system of N-3 is used. According to this, even in a system in which a retarder is added at the same time, aluminum chloride or iron nitrate (Fe
It can be seen that the initiator effect of ³⁺ ) is exhibited.

[Embodiment 2] Although the cement paste is described in the above Embodiment 1, the case of concrete is described in this embodiment. As the cement, N-3 [normal Portland cement manufactured by Chichibu Cement Co., Ltd.] shown in [Table 1] and [Table 2] was used.

Further, citric acid was used as the retarder, and tap water was used as the kneading water. As the initiator, magnesium nitrate, aluminum chloride, iron chloride (Fe ³⁺ ) and iron nitrate (Fe ³⁺ ) were used. Then, using the mixture shown in [Table 14], a 55 L pan-type forced kneading mixer was used for kneading, and the coarse aggregate, the cement, and the fine aggregate were added in this order, and the kneading was performed for 20 seconds. After that, add water, mix for 1 minute, scrape off for 1 minute and add retarder,
Kneading was continued for 1 minute, the kneaded concrete was discharged into a boat, covered with a sheet, and allowed to stand. After 6 hours from the contact with water, the concrete was returned to the mixer, the initiator was added as a powder, and the mixture was kneaded for 1 minute and scraped for 30 seconds, and again mixed for 1 minute. The temperature is 20
It was ± 1 ° C.

Table 14 Slump Water Cement Ratio Fine Aggregate Ratio Water Cement Fine Aggregate Coarse Aggregate (cm) (%) (%) (kg / m ³ ) (kg / m ³ ) (kg / m ³ ) (kg / m ³ ) 12 55.0 48.0 180 327 878 977 The setting test was performed according to JIS A 6204 Annex 1 "Setting method for setting time of concrete". The temperature was 20 ± 1 ° C.

[Table 15] shows that citric acid (addition amount is 0.1
25%) only after addition, citric acid (addition amount 0.125
%) Shows the setting time of concrete when an initiator was added to the system after 6 hours of contact with water. Table 15 Addition amount of initiator Coagulation time (hour-minute) Start-time termination Mg (NO ₃ ) ₂₀ % (no addition) 19-35 22-45 1.0% 8-20 12-00 2.0% 6-50 10-30 3.0% 5-35 9-10 AlCl ₃ 0.5% 10-00 13-05 1.0% 6-35 10-00 1.5% 6-00 9-15 5.0% 7-25 9-35 FeCl ₃ 2.0% 5 -10 7-10 Fe (NO ₃ ) ₃ 0.5% 10-25 14-00 1.0% 8-40 12-50 2.0% 8-05 11-50 5.0% 12-45 17-50 * Both retarder and initiator In the system not used, the setting time from contact with water was 5 hours 55 minutes for the first start and 8 hours 10 minutes for the end. According to this, 0.125% citric acid
If magnesium nitrate, aluminum chloride, iron chloride (Fe ³⁺ ) or iron nitrate (Fe ³⁺ ) is added as an initiator to the concrete whose addition has been postponed and the termination has been extended to approximately 23 hours, the setting time of the concrete can be increased. It can be seen that it is shortened and shows a good initiation action.

[0034]

[Effects] According to the present invention, it is possible to freely control the time when the setting of the cement-based material starts. As a result, for example, planned operation of the ready-mixed concrete plant can be performed. Further, restrictions on transportation time are greatly released, it becomes possible to install a ready-mixed concrete factory in a distant place, and it becomes possible to consolidate the ready-mixed concrete factory, so that the cost can be reduced. It can also be effectively transported to remote islands by sea.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C04B 24/04 24/10 24/12 Z // C04B 103: 22 (72) Inventor Yoshiko Shoko Saitama Chichibu Cement Co., Ltd. Central Research Institute, 2-1-1 Tsukimi-cho, Kumagaya-shi, Japan (72) Inventor Mitsuo Tanaka 2-1-1 Tsukimi-cho, Kumagaya-shi, Saitama Central Research Institute of Chichibu Cement Co., Ltd.

Claims (5)

[Claims] 1. Used for controlling the setting of cement-based materials
An agent comprising a setting retarder and a setting initiator,
The setting initiator is Li⁺, Mg²⁺, Mn²⁺, Ba ²⁺, A
l³⁺, Fe³⁺, Ti⁴⁺And Sn⁴⁺Chosen from a group of
Cemene characterized by being a substance that provides metal ions
A coagulation control agent for G-based materials. 2. The setting control agent for cementitious materials according to claim 1, wherein the substance providing metal ions is nitrate, sulfate or chloride. 3. A setting retarder selected from the group consisting of oxycarboxylic acid, oxycarboxylic acid salt, aminocarboxylic acid, aminocarboxylic acid salt, saccharide, zinc compound, silicofluoride, boric acid and borate salt. The setting control agent for cementitious materials according to claim 1, wherein 4. A method for controlling the setting of a cement-based material, which comprises adding a setting retarder to the cement-based material and delaying the setting time thereof as compared with the case where no addition is made, and then adding Li ⁺ , Mg ²⁺ ,
A method for controlling the setting of a cement material, which comprises adding a substance that provides a metal ion selected from the group of Mn ²⁺ , Ba ²⁺ , Al ³⁺ , Fe ³⁺ , Ti ⁴⁺ and Sn ⁴⁺ . 5. A method for controlling the setting of a cement-based material, which comprises adding a setting retarder to the cement-based material and delaying the setting time thereof as compared with the case where no addition is made, and then adding Li ⁺ , Mg ²⁺ ,
Mn ²⁺ , Ba ²⁺ , Al ³⁺ , Fe ³⁺ , Ti ⁴⁺ and Sn ⁴⁺ A substance that provides a metal ion selected from the group is used to predict the release of the setting delay, and a predetermined amount of the substance at a predetermined time. A method for controlling the setting of a cement-based material, which comprises adding