Drying shrinkage reduction method of cement-based hardened body

Abstract

The present invention is to provide an economical and efficient method of reducing drying shrinkage of a cement-based hardened body without requiring the cost and/or the labor and time. A cement-based hardened body is impregnated with a solution containing urea or a solution containing sulfate together with urea. An impregnation treatment may be by a method of coating or spraying the cement-based hardened body with the solution, or alternatively, immersing the cement-based hardened body in the solution containing both urea and sulfate for a predetermined period of time. The solution containing both urea and sulfate may be a solution prepared simply by dissolving both urea and sulfate in water. Besides, there are no particular limitations on a liquid allowing dissolution of both urea and sulfate, so long as it causes no impairment of a drying shrinkage reduction effect, and therefore, a solution having the drying shrinkage reduction effect in itself is also applicable for use of a solution containing both urea and sulfate in a state of being dissolved in such solution.

Claims

1. A method of reducing drying shrinkage of a cement-based hardened body comprising: demolding a cement-based hardened body; and impregnating a surface of the cement-based hardened body with a solution containing urea within seven days after the demolding.

2. The method according to claim 1, wherein said solution containing urea is prepared by dissolving urea in water, a nonionic surfactant or a mixture of the nonionic surfactant and the water.

3. The method according to claim 1, wherein the cement-based hardened body is impregnated with said solution containing urea by coating the surface of the cement-based hardened body after the demolding with said solution containing urea.

4. The method according to claim 1, wherein a urea concentration in said solution is not less than 20 mass %.

5. The method according to claim 1, wherein a urea concentration in said solution is in the range of 30 to 60 mass %.

6. The method according to claim 1, wherein the solution further comprises sulfate.

7. The method according to claim 6, wherein the drying shrinkage of the cement-based hardened body is 0.058% in length or less.

8. The method according to claim 6, wherein said solution containing both urea and sulfate is prepared by dissolving urea and sulfate in water, a nonionic surfactant or a mixture of the nonionic surfactant and the water.

9. The method according to claim 6, wherein the cement-based hardened body is impregnated with said solution containing both urea and sulfate by coating the surface of the cement-based hardened body with said solution containing both urea and sulfate.

10. The method according to claim 6, wherein a urea concentration in said solution is not less than 20 mass %.

11. The method according to claim 10, wherein a sulfate concentration in said solution is not less than 1 mass %.

12. The method according to claim 6, wherein a urea concentration in said solution is in the range of 30 to 60 mass %.

13. The method according to claim 12, wherein a sulfate concentration in said solution is in the range of 3 to 15 mass %.

14. The method according to claim 13, wherein a mass ratio of urea to sulfate in said solution is in the range of 10:1 to 4:1.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 is a graph showing a relation between an age (days) and a length change rate (%) in an experiment 1-1 (a water/cement ratio of 40%).

(2) FIG. 2 is a graph showing a relation between an age (days) and a length change rate (%) in an experiment 1-2 (a water/cement ratio of 60%).

(3) FIG. 3 is a graph showing a relation between an age (days) and a length change rate (%) in an experiment 1-3 on the basis of comparison results obtained when changing a urea concentration, in regard to an impregnation treatment given with urea on the third day after demolding.

(4) FIG. 4 is a graph showing a relation between an age (days) and a length change rate (%) in the experiment 1-3 on the basis of comparison results obtained when changing a urea concentration, in regard to an impregnation treatment given with urea on the seventh day after demolding.

(5) FIG. 5 is a graph showing a relation between an age (days) and a length change rate (%) in the experiment 1-3 on the basis of comparison results obtained when changing a urea solution immersion time, in regard to an impregnation treatment given with urea on the third day after demolding.

(6) FIG. 6 is a graph showing a relation between an age (days) and a length change rate (%) in the experiment 1-3 on the basis of comparison results obtained when changing a urea solution immersion time, in regard to an impregnation treatment given with urea on the seventh day after demolding.

(7) FIG. 7 is a graph showing a relation between an age (days) and a length change rate (%) in the experiment 1-3, in regard to an impregnation treatment with a commercially-available drying shrinkage reducing agent solution and that with an aqueous solution of a commercially-available premixed cross-section restoring mortar material, as comparative examples.

(8) FIG. 8 is a graph showing a relation between an age (days) and a length change rate (%) in the experiment 1-3, in regard to an impregnation treatment with a solution prepared by dissolving urea in an aqueous solution of a commercially-available premixed cross-section restoring material and that with a solution prepared by dissolving urea in a mixture of a commercially-available drying shrinkage reducing agent solution and the above aqueous solution.

(9) FIG. 9 is a graph showing a relation between an age (days) and a length change rate (%) in an experiment 2-1 (a water/cement ratio of 40%).

(10) FIG. 10 is a graph showing a relation between an age (days) and a length change rate (%) in an experiment 2-2 (a water/cement ratio of 60%).

(11) FIG. 11 is a graph showing a relation between an age (days) and a length change rate (%) in an experiment 2-3 (a water/cement ratio of 50%) when changing a sodium sulfate solution immersion time (on the third day after demolding).

(12) FIG. 12 is a graph showing a relation between an age (days) and a length change rate (%) in the experiment 2-3 (a water/cement ratio of 50%) when changing a sodium sulfate concentration.

(13) FIG. 13 is a graph showing a relation between an age (days) and a length change rate (%) in the experiment 2-3 (a water/cement ratio of 50%) when changing a sodium sulfate solution immersion time (on the seventh day after demolding).

(14) FIG. 14 is a graph showing a relation between an age (days) and a length change rate (%) in an experiment 3-1 (a water/cement ratio of 40%).

(15) FIG. 15 is a graph showing a relation between an age (days) and a length change rate (%) in an experiment 3-2 (a water/cement ratio of 60%).

(16) FIG. 16 is a graph showing a relation between an age (days) and a length change rate (%) in an experiment 3-3 (a water/cement ratio of 50%) when changing an immersion time (on the third day after demolding).

(17) FIG. 17 is a graph showing a relation between an age (days) and a length change rate (%) in the experiment 3-3 (a water/cement ratio of 50%) when changing an immersion time (on the seventh day after demolding).

(18) FIG. 18 is a graph showing a relation between an age (days) and a length change rate (%) in an experiment 4-1 (a water/cement ratio of 40%).

(19) FIG. 19 is a graph showing a relation between an age (days) and a length change rate (%) in an experiment 4-2 (a water/cement ratio of 60%).

DESCRIPTION OF EMBODIMENTS

(20) Hereinafter will be described specific examples of a drying shrinkage reduction method of a cement-based hardened body according to the present invention with reference to the following experiments conducted to confirm the resultant effects, as compared with those based on comparative examples.

Example 1

(21) Firstly, an example 1 will be described on a drying shrinkage reduction effect resulting from an impregnation treatment given to the surface of a cement-based hardened body after demolding with a solution containing urea (a solution containing no sulfate) (experiments 1-1 to 1-3).

(22) (Experiment 1-1)

(23) An experiment 1-1 was conducted to confirm the effects resulting from an impregnation treatment given to a usual mortar hardened body having a water/cement ratio of 40% with water containing urea.

(24) (1) Experimental Conditions

(25) Conditions of the experiment are shown on a table 1 below.

(26) TABLE-US-00001 TABLE 1 Target flow value Immersion Immersion (15 times Immersion time date (after w/c s/c of rodding) condition (min) demolding) Symbol 40% 1.2 200 10 (mm) None N Water 1 Third day 3rd-day water Seventh day 7th-day water 50% urea 1 Third day 3rd-day urea Seventh day 7th-day urea

(27) Wherein

(28) c: Ordinary portland cement,

(29) w: Water,

(30) s: River sand, and
Urea concentration=urea(g)/(urea(g)+water(g))=50%

(31) Symbols given to specimens in the table 1 represent the following conditions respectively.

(32) N: No impregnation treatment

(33) 3rd-day water: Immersion of specimen in water for one minute on the third day after demolding

(34) 7th-day water: Immersion of specimen in water for one minute on the seventh day after demolding

(35) 3rd-day urea: Immersion of specimen in solution containing urea at concentration of 50% for one minute on the third day after demolding

(36) 7th-day urea: Immersion of specimen in solution containing urea at concentration of 50% for one minute on the seventh day after demolding

(37) The experiment 1-1 was conducted also to examine whether or not the resultant effects based on urea are affected by a water immersion treatment (first immersion) given to each specimen at the age of 91 days (13 weeks) and a water re-immersion treatment (second immersion) given to each specimen at the age of 119 days (17 weeks).

(38) (2) Experimental Results

(39) Results of the experiment are shown in FIG. 1.

(40) FIG. 1 is a graph showing an age (days) after demolding on its horizontal axis and a length change rate (%) on is vertical axis.

(41) A specimen (N) given no impregnation treatment resulted in about a 0.112% reduction in the length by the age of 91 days due to drying shrinkage, and afterwards, the length thereof was maintained approximately constant.

(42) A specimen (3rd-day water) immersed in water for one minute on the third day after demolding resulted in about a 0.106% reduction in the length by the age of 91 days due to drying shrinkage, wherein although a recovery of the length to about 0.082% in the length change rate was once allowed thanks to the first immersion, the length change rate came to be about 0.110% at the age of 119 days due to the rapid progressing of the drying shrinkage following such recovery of the length, and further, although a recovery of the length to about 0.092% in the length change rate was once allowed thank to the second immersion, the length change rate at the age of 147 days (21 weeks) came to be about 0.112% as being approximately equal to that of the specimen (N), and further, that at the age of 182 days (26 weeks) came to be about 0.120% as being greater than that of the specimen (N).

(43) A specimen (7th-day water) immersed in water for one minute on the seventh day after demolding resulted in about a 0.114% reduction in the length by the age of 91 days due to drying shrinkage, wherein although a recovery of the length to about 0.087% in the length change rate was once allowed thanks to the first immersion, the length change rate came to be about 0.119% at the age of 119 days due to the rapid progressing of the drying shrinkage following such recovery of the length, and further, although a recovery of the length to about 0.100% in the length change rate was once allowed thanks to the second immersion, the length change rate at the age of 147 days (21 weeks) and that at the age of 182 days (26 weeks) respectively came to be about 0.123% and about 0.132% as being greater than that of the specimen (N).

(44) A specimen (3rd-day urea) immersed in a solution containing urea at a concentration of 50% for one minute on the third day after demolding resulted in about a 0.090% reduction in the length by the age of 91 days due to drying shrinkage, wherein although a recovery of the length to about 0.066% in the length change rate was once allowed thanks to the first immersion, the length change rate came to be about 0.089% at the age of 119 days due to the rapid progressing of the drying shrinkage following such recovery of the length, and further, although a recovery of the length to about 0.072% in the length change rate was once allowed thanks to the second immersion, the length change rate at the age of 147 days (21 weeks) and that at the age of 182 days (26 weeks) were respectively about 0.090% and about 0.098%.

(45) A specimen (7th-day urea) immersed in a solution containing urea at a concentration of 50% for one minute on the seventh day after demolding resulted in about a 0.090% reduction in the length by the age of 91 days due to drying shrinkage, wherein although a recovery of the length to about 0.075% in the length change rate was once allowed thanks to the first immersion, the length change rate came to be about 0.100% in the length change rate by the age of 119 days due to the rapid progressing of the drying shrinkage following such recovery of the length, and further, although a recovery of the length to about 0.085% in the length change rate was once allowed thanks to the second immersion, the length change rate at the age of 147 days (21 weeks) and that at the age of 182 days (26 weeks) were respectively about 0.102% and about 0.110%.

(46) (3) Conclusions

(47) It is confirmed by the experiment 1-1 that the impregnation treatment given to the surface of the mortar hardened body with the solution prepared by dissolving the urea in water allows about a 10 to 20% reduction in the drying shrinkage of the hardened body to be obtained, as compared with the case of no impregnation treatment and/or the impregnation treatment with water.

(48) Incidentally, as to whether or not the drying shrinkage reduction effect is affected by the water immersion treatment given at the age of 91 days and the age of 119 days, it is confirmed that a gap in the length change rate between the specimens (3rd-day urea) and (7th-day urea) has somewhat widened.

(49) (Experiment 1-2)

(50) An experiment 1-2 was conducted to confirm the effects resulting from an impregnation treatment given to a usual mortar hardened body having a water/cement ratio of 60% with water containing urea.

(51) (1) Experimental Conditions

(52) Conditions of the experiment are shown on a table 2 below.

(53) TABLE-US-00002 TABLE 2 Target flow value Immersion Immersion (15 times Immersion time date (after w/c s/c of rodding) condition (min) demolding) Symbol 60% 2.4 200 10 (mm) None N Water 1 Third day 3rd-day water Seventh day 7th-day water 50% urea 1 Third day 3rd-day urea Seventh day 7th-day urea

(54) Wherein

(55) c: Ordinary portland cement

(56) w: Water

(57) s: River sand
Urea concentration=urea(g)/(urea(g)+water(g))=50%

(58) Symbols given to specimens in the Table 2 represent the following conditions respectively.

(59) N: No impregnation treatment

(60) 3rd-day water: Immersion of specimen in water for one minute on the third day after demolding

(61) 7th-day water: Immersion of specimen in water for one minute on the seventh day after demolding

(62) 3rd-day urea: Immersion of specimen in solution containing urea at concentration of 50% for one minute on the third day after demolding

(63) 7th-day urea: Immersion of specimen in solution containing urea at concentration of 50% for one minute on the seventh day after demolding

(64) The experiment 1-2 was conducted also to examine whether or not the resultant effects based on urea are affected by a water immersion treatment (first immersion) given to each specimen at the age of 91 days (13 weeks) and a water re-immersion treatment (second immersion) given to each specimen at the age of 119 days (17 weeks).

(65) (2) Experimental Results

(66) Results of the experiment are shown in FIG. 2.

(67) FIG. 2 is a graph showing an age (days) after demolding on its horizontal axis and a length change rate (%) on its vertical axis.

(68) A specimen (N) given no impregnation treatment resulted in about a 0.108% reduction in the length by the age of 91 days due to drying shrinkage, and there was a length change to about 0.112% in the length change rate at the age of 147 days (21 weeks).

(69) A specimen (3rd-day water) immersed in water for one minute on the third day after demolding resulted in about a 0.104% reduction in the length by the age of 91 days due to drying shrinkage, wherein although a recovery of the length to about 0.083% in the length change rate was once allowed thanks to the first immersion, the length change rate came to be about 0.109% at the age of 119 days due to the rapid progressing of the drying shrinkage following such recovery of the length, and further, although a recovery of the length to about 0.087% in the length change rate was once allowed thanks to the second immersion, the length change rate at the age of 147 days (21 weeks) came to be about 0.114% as being approximately equal to that of the specimen (N), and further, that at the age of 182 days (26 weeks) came to be about 0.121% as being greater than that of the specimen (N).

(70) A specimen (7th-day water) immersed in water for one minute on the seventh day after demolding resulted in about a 0.112% reduction in the length by the age of 91 days due to drying shrinkage, wherein although a recovery of the length to about 0.088% in the length change rate was once allowed thanks to the first immersion, the length change rate came to be about 0.117% at the age of 119 days due to the rapid progressing of the drying shrinkage following such recovery of the length, and further, although a recovery of the length to about 0.094% in the length change rate was once allowed thanks to the second immersion, the length change rate at the age of 147 days (21 weeks) and that at the age of 182 days (26 weeks) respectively came to be about 0.122% and about 0.130% as being greater than that of the specimen (N).

(71) A specimen (3rd-day urea) immersed in a solution containing urea at a concentration of 50% for one minute on the third day after demolding resulted in about a 0.072% reduction in the length by the age of 91 days due to drying shrinkage, wherein although a recovery of the length to about 0.052% in the length change rate was once allowed thanks to the first immersion, the length change rate came to be about 0.076% at the age of 119 days due to the rapid progressing of the drying shrinkage following such recovery of the length, and further, although a recovery of the length to about 0.055% in the length change rate was once allowed thanks to the second immersion, the length change rate at the age of 147 days (21 weeks) and that at the age of 182 days (26 weeks) were respectively about 0.077% and about 0.086%.

(72) A specimen (7th-day urea) immersed in a solution containing urea at a concentration of 50% for one minute on the seventh day after demolding resulted in about a 0.078% reduction in the length by the age of 91 days due to drying shrinkage, wherein although a recovery of the length to about 0.058% in the length change rate was once allowed thanks to the first immersion, the length change rate came to be about 0.078% at the age of 119 days due to the rapid progressing of the drying shrinkage following such recovery of the length, and further, although a recovery of the length to about 0.060% in the length change rate was once allowed thanks to the second immersion, the length change rate at the age of 147 days (21 weeks) and that at the age of 182 days (26 weeks) were respectively about 0.080% and about 0.088%.

(73) (3) Conclusions

(74) It is confirmed by the experiment 1-2 that the impregnation treatment given to the surface of the mortar hardened body with the solution prepared by dissolving the urea in water allows about a 30% reduction in the drying shrinkage of the hardened body to be obtained, as compared with the case of no impregnation treatment and/or the impregnation treatment with water.

(75) Incidentally, as to whether or not the drying shrinkage reduction effect is affected by the water immersion treatment given at the age of 91 days and the age of 119 days, it is confirmed that a gap in the length change rate between the specimens (3rd-day urea) and (7th-day urea) has somewhat narrowed.

(76) (Experiment 1-3)

(77) An experiment 1-3 was conducted to confirm the effects obtained further when changing a urea concentration, when changing a urea solution immersion time and when dissolving urea in a liquid other than water, with reference to the results of the experiments 1-1 and 1-2.

(78) (1) Experimental Conditions

(79) Conditions of the experiment are shown on a table 3 below.

(80) TABLE-US-00003 TABLE 3 Target flow value Immersion Immersion (15 times Immersion time date (after w/c s/c of rodding) condition (min) demolding) Symbol 60% 1.7 200 10 (mm) None N Water 1 Third day 3rd-day water Seventh day 7th-day water 10 Third day 3rd-day water 10 min Seventh day 7th-day water 10 min 30 Third day 3rd-day water 30 min Seventh day 7th-day water 30 min 30% urea 1 Third day 3rd-day 30%-urea Seventh day 7th-day 30%-urea 40% urea 1 Third day 3rd-day 40%-urea Seventh day 7th-day 40%-urea 50% urea 1 Third day 3rd-day 50%-urea Seventh day 7th-day 50%-urea 10 Third day 3rd-day 50%-urea 10 min Seventh day 7th-day 50%-urea 10 min 30 Third day 3rd-day 50%-urea 30 min Seventh day 7th-day 50%-urea 30 min NG 1 Third day 3rd-day NG Seventh day 7th-day NG NF1000 1 Third day 3rd-day NF1000 Seventh day 7th-day NF1000 Urea + 1 Third day 3rd-day urea + NF NF1000 Seventh day 7th-day urea + NF Urea + 1 Third day 3rd-day urea + NF + NG NF1000 + NG Seventh day 7th-day urea + NF + NG

(81) Wherein

(82) c: Ordinary portland cement

(83) w: Water

(84) s: River sand
Urea concentration=urea(g)/urea(g)+water,NG or NF1000(g))

(85) NG: Product by Flowric Co., Ltd, under the trade name Nutte-guard (a registered trademark)

(86) NF1000: Dilute solution prepared by diluting a material, which is by DPS Bridge Works Co., Ltd, under the trade name Naoshitaru NF (Naoshitaru is a registered trademark), 1000 times (a weight ratio) with water

(87) It is noted that the above material Naoshitaru NF is commercially available as a premixed cross-section restoring mortar material prepared by adding components such as nylon fibers and a nonionic surfactant for drying shrinkage reduction to main powder components such as ordinary cement, silica fume and blast furnace slag fine powder.

(88) Symbols given to specimens in the table 3 represent the following conditions respectively.

(89) N: No impregnation treatment

(90) 3rd-day water: Immersion of specimen in water for one minute on the third day after demolding

(91) 7th-day water: Immersion of specimen in water for one minute on the seventh day after demolding

(92) 3rd-day water 10 min: Immersion of specimen in water for 10 minutes on the third day after demolding

(93) 7th-day water 10 min.: Immersion of specimen in water for 10 minutes on the seventh day after demolding

(94) 3rd-day water 30 min: Immersion of specimen in water for 30 minutes on the third day after demolding

(95) 7th-day water 30 min: Immersion of specimen in water for 30 minutes on the seventh day after demolding

(96) 3rd-day 30%-urea: Immersion of specimen in solution containing urea at concentration of 30% for one minute on the third day after demolding

(97) 7th-day 30%-urea: Immersion of specimen in solution containing urea at concentration of 30% for one minute on the seventh day after demolding

(98) 3rd-day 40%-urea: Immersion of specimen in solution containing urea at concentration of 40% for one minute on the third day after demolding

(99) 7th-day 40%-urea: Immersion of specimen in solution containing urea at concentration of 40% for one minute on the seventh day after demolding

(100) 3rd-day 50%-urea: Immersion of specimen in solution containing urea at concentration of 50% for one minute on the third day after demolding

(101) 7th-day 50%-urea: Immersion of specimen in solution containing urea at concentration of 50% for one minute on the seventh day after demolding

(102) 3rd-day 50%-urea 10 min: Immersion of specimen in solution containing urea at concentration of 50% for 10 minutes on the third day after demolding

(103) 7th-day 50%-urea 10 min: Immersion of specimen in solution containing urea at concentration of 50% for 10 minutes on the seventh day after demolding

(104) 3rd-day 50%-urea 30 min: Immersion of specimen in solution containing urea at concentration of 50% for 30 minutes on the third day after demolding

(105) 7th-day 50%-urea 30 min: Immersion of specimen in solution containing urea at concentration of 50% for 30 minutes on the seventh day after demolding

(106) 3rd-day NG: Immersion of specimen in NG solution for one minute on the third day after demolding

(107) 7th-day NG: Immersion of specimen in NG solution for one minute on the seventh day after demolding

(108) 3rd-day NF: Immersion of specimen in NF-1000 solution for one minute on the third day after demolding

(109) 7th-day NF: Immersion of specimen in NF-1000 solution for one minute on the seventh day after demolding

(110) 3rd-day urea+NF: Immersion of specimen in NF-1000 solution containing urea at concentration of 50% for one minute on the third day after demolding

(111) 7th-day urea+NF: Immersion of specimen in NF-1000 solution containing urea at concentration of 50% for one minute on the seventh day after demolding
Urea concentration=urea(g)/(urea(g)+NF1000(g))

(112) 3rd-day urea+NF+NG: Immersion of specimen in mixture of NF-1000 solution containing urea at concentration of 50% and NG solution for one minute on the third day after demolding

(113) 7th-day urea+NF+NG: Immersion of specimen in mixture of NF-1000 solution containing urea at concentration of 50% and NG solution for one minute on the seventh day after demolding
Urea concentration=urea(g)/urea(g)+NF1000(g)+NG(g))
NF1000 (g)=NG (g)

(114) The experiment 1-3 was conducted also to examine whether or not the resultant effects based on urea are affected by a water immersion treatment (first immersion) given to each specimen at the age of 91 days (13 weeks) and a water re-immersion treatment (second immersion) given to each specimen at the age of 119 days (17 weeks).

(115) (2) Experimental Results

(116) Results of the experiment are shown in FIGS. 3 to 7.

(117) FIG. 3 is a graph showing a relation between an age (days) and a length change rate (%) in the experiment 1-3 when changing a urea concentration (3rd-day 30%-urea, 3rd-day 40%-urea and 3rd-day 50%-urea), in regard to an impregnation treatment given with urea on the third day after demolding.

(118) At the point of the age of 91 days (13 weeks), a drying shrinkage reduction effect of about 23% was found in the specimens 3rd-day 30%-urea and 3rd-day 40%-urea, while that of about 33% was found in the specimen 3rd-day 50%-urea.

(119) At the point of the age of 119 days (17 weeks) after two times of the water immersion treatment in the middle of the experiment, there were a drying shrinkage reduction effect of about 27% in the specimen 3rd-day 30%-urea, that of about 30% in the specimen 3rd-day 40%-urea and that of about 37% in the specimen 3rd-day 50%-urea.

(120) The result was a remarkable difference in the drying shrinkage reduction effect between the condition of 30% urea concentration and that of 50% urea concentration, while a difference in the drying shrinkage reduction effect between the condition of 30% urea concentration and that of 40% urea concentration was not remarkable.

(121) FIG. 4 is a graph showing a relation between an age (days) and a length change rate (%) in the experiment 1-3 when changing a urea concentration (7th-day 30%-urea, 7th-day 40%-urea and 7th-day 50%-urea), in regard to an impregnation treatment given with urea on the seventh day after demolding.

(122) At the point of the age of 91 days (13 weeks), a drying shrinkage reduction effect of about 9% was found in the specimen 7th-day 30%-urea, that of about 6% was found in the specimen 7th-day 40%-urea, and that of about 19% was found in the specimen 7th-day 50%-urea.

(123) At the point of the age of 119 days (17 weeks) after two times of the water immersion treatment in the middle of the experiment, there were a drying shrinkage reduction effect of about 9% in the specimen 7th-day 30%-urea, that of about 11% in the specimen 7th-day 40%-urea and that of about 16% in the specimen 7th-day 50%-urea.

(124) Meanwhile, for the impregnation treatment given with the urea on the seventh day after demolding, the result was also a remarkable difference in the drying shrinkage reduction effect between the condition of 30% urea concentration and that of 50% urea concentration, while a difference in the drying shrinkage reduction effect between the condition of 30% urea concentration and that of 40% urea concentration was not remarkable, and further, there was a tendency similar to that shown in the impregnation treatment given with the urea on the third day after demolding.

(125) However, as to the drying shrinkage reduction effect, a greater effect is exhibited in the case of the impregnation treatment given with the urea on the third day after demolding, as compared with the impregnation treatment given with the urea on the seventh day after demolding.

(126) FIG. 5 is a graph showing a relation between an age (days) and a length change rate (%) in the experiment 1-3 when changing an immersion time, with the urea concentration controlled to 50% (3rd-day 50%-urea, 3rd-day 50%-urea 10 min, and 3rd-day 50%-urea 30 min), in regard to an impregnation treatment given with urea on the third day after demolding, in contrast to the specimens (3rd-day water, 3rd-day water 10 min and 3rd-day water 30 min) immersed in water containing no urea.

(127) Referring to the specimens immersed in water containing no urea, there was almost no difference in the length change rate between the specimen 3rd-day water (immersed for one minute) and the specimen 3rd-day water 10 min, whereas an increase in the length change rate was found in the specimen 3rd-day water 30 min. This shows that the water immersion treatment for a long period of time causes the drying shrinkage after hardening to get larger, in cases where the specimen was given the water immersion treatment relatively early as soon as the third day after demolding.

(128) Meanwhile, for the specimens immersed in water containing the urea (at the urea concentration of 50%), it is found that as the immersion time becomes longer in the order of one minute, 10 minutes and 30 minutes, a greater drying shrinkage reduction effect is obtained. This seems to be because the immersion treatment was given in a state where the urea is allowed to permeate the hardened body inwards more deeply from its surface.

(129) FIG. 6 is a graph showing a relation between an age (days) and a length change rate (%) in the experiment 1-3 when changing an immersion time, with the urea concentration controlled to 50% (7th-day 50%-urea, 7th-day 50%-urea 10 min and 7th-day 50%-urea 30 min), in regard to an impregnation treatment given with urea on the seventh day after demolding, in contrast to the specimens (7th-day water, 7th-day water 10 min and 7th-day water 30 min) immersed in water containing no urea.

(130) Referring to the specimens immersed in water containing no urea, there was no remarkable difference in the length change rate among the specimens 7th-day water (immersed for one minute), 7th-day water 10 min and 7th-day water 30 min.

(131) Meanwhile, for the specimens immersed in water containing the urea (at the urea concentration of 50%), it is found that as the immersion time becomes longer in the order of one minute, 10 minutes and 30 minutes, a greater drying shrinkage effect is obtained, like the impregnation treatment given with the urea on the third day after demolding, while for the specimen 7th-day 50%-urea having a short immersion time as much as one minute, such specimen was greatly different in the drying shrinkage reduction effect from the specimen 3rd-day 50%-urea allowing more exhibition of the drying shrinkage reduction effect as shown in FIG. 5, whereas differences in the drying shrinkage reduction effect between the specimens 7th-day 50%-urea 10 min and 7th-day 50%-urea 30 min and the specimens 3rd-day 50%-urea 10 min and 3rd-day 50%-urea 30 min shown in FIG. 5 have been gradually reduced.

(132) FIG. 7 is a graph showing a relation between an age (days) and a length change rate (%) in the experiment 1-3 on the basis of comparison results obtained in regard to an impregnation treatment with a commercially-available drying shrinkage reducing agent solution and that with an aqueous solution of a commercially-available premixed cross-section restoring mortar material (3rd-day NG, 7th-day NG, 3rd-day NF and 7th-day NF).

(133) Referring to the specimens 3rd-day NG and 7th-day NG both using a coating-type drying shrinkage reducing agent solution, the drying shrinkage reduction effect was found, in contrast to the specimen N given no impregnation treatment, while such effect was nearly equal to that of the specimen 3rd-day 50%-urea in FIG. 3 and that of the specimen 7th-day 50%-urea in FIG. 4 both having the same other conditions as the specimens 3rd-day NG and 7th-day NG.

(134) Referring to the specimen 3rd-day NF and 7th-day NF both prepared by diluting a commercially-available cross-section restoring mortar material 1000 times (a weight ratio) with water, there was no remarkable difference in the drying shrinkage reduction effect between these specimens and the specimen N given no impregnation treatment.

(135) FIG. 8 is a graph showing a relation between an age (days) and a length change rate (%) in the experiment 1-3, in regard to an impregnation treatment with a solution prepared by dissolving urea in an aqueous solution of a commercially-available premixed cross-section restoring material and that with a solution prepared by dissolving urea in a mixture of a commercially-available drying shrinkage reducing agent solution and the above aqueous solution (3rd-day urea+NF, 7th-day urea+NF, 3rd-day urea+NF+NG, and 7th-day urea+NF+NG).

(136) The result was that the drying shrinkage reduction effect is confirmed even when using the solution prepared by dissolving the urea in the solution other than the water, while for the mortar used in the experiment 1-3, there was no remarkable difference in the drying shrinkage reduction effect between the condition of using water and that of using the solution other than water.

(137) (3) Conclusions

(138) As the result of comparison in various cases on the urea concentration, the immersion time and the application of dissolution of the urea in the solution other than water, it is confirmed by the experiment 1-3 that there is a tendency to obtain a greater drying shrinkage reduction effect, as the urea concentration becomes higher, and the immersion time becomes longer. It is also confirmed that a higher urea concentration and a longer immersion time result in lessening in influences of the number of days spent from demolding to the immersion treatment.

COMPARATIVE EXAMPLES

(139) Comparative examples will now be described on a drying shrinkage reduction effect resulting from an impregnation treatment given to the surface of a cement-based hardened body after demolding with a solution containing sulfate (experiments 2-1 to 2-3).

(140) (Experiment 2-1)

(141) An experiment 2-1 was conducted to confirm the presence/absence of the effects resulting from an impregnation treatment given to a usual mortar hardened body having a water/cement ratio of 40% with water containing sodium sulfate Na.sub.2SO.sub.4 which is a type of metal sulfate.

(142) (1) Experimental Conditions

(143) Conditions of the experiment are shown on a table 4 below.

(144) TABLE-US-00004 TABLE 4 Target flow value Immersion Immersion (15 times Immersion time date (after w/c s/c of rodding) condition (min) demolding) Symbol 40% 1.2 200 10 (mm) None N Water 1 Third day 3rd-day water Seventh day 7th-day water 10% Na.sub.2SO.sub.4 1 Third day 3rd-day sulfate Seventh day 7th-day sulfate

(145) Wherein

(146) c: Ordinary portland cement

(147) w: Water

(148) s: River sand
Na.sub.2SO.sub.4 concentration=Na.sub.2SO.sub.4(g)/(Na.sub.2SO.sub.4(g)+water(g))=10%

(149) Symbols given to specimens in the table 4 represent the following conditions respectively.

(150) N: No impregnation treatment

(151) 3rd-day water: Immersion of specimen in water for one minute on the third day after demolding

(152) 7th-day water: Immersion of specimen in water for one minute on the seventh day after demolding

(153) 3rd-day sulfate: Immersion of specimen in solution containing Na.sub.2SO.sub.4 at concentration of 10% for one minute on the third day after demolding

(154) 7th-day sulfate: Immersion of specimen in solution containing Na.sub.2SO.sub.4 at concentration of 10% for one minute on the seventh day after demolding

(155) The experiment 2-1 was conducted in the case of a water/cement ratio of 40% to examine whether or not the resultant effects based on sulfate (sodium sulfate Na.sub.2SO.sub.4) are affected by a water immersion treatment given to each specimen every week in the period from the age of 28 days (4 weeks) to the age of 91 days (13 weeks).

(156) (2) Experimental Results

(157) Results of the experiment are shown in FIG. 9.

(158) FIG. 9 is a graph showing an age (days) after demolding on its horizontal axis and a length change rate (%) at its vertical axis.

(159) A specimen (N) given no impregnation treatment resulted in about a 0.116% reduction in the length by the age of 91 days due to drying shrinkage.

(160) A specimen (3rd-day water) immersed in water for one minute on the third day after demolding resulted in about a 0.096% reduction in the length by the age of 91 days (13 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(161) A specimen (7th-day water) immersed in water for one minute on the seventh day after demolding resulted in about a 0.097% reduction in the length by the age of 91 days (13 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(162) A specimen (3rd-day sulfate) immersed in a solution containing Na.sub.2SO.sub.4 at a concentration of 10% for one minute on the third day after demolding resulted in about a 0.099% reduction in the length by the age of 91 days (13 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(163) A specimen (7th-day sulfate) immersed in a solution containing Na.sub.2SO.sub.4 at a concentration of 10% for one minute on the seventh day after demolding resulted in about a 0.093% reduction in the length by the age of 91 days (13 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(164) (3) Conclusions

(165) As the result of comparison in drying shrinkage and hardening of the hardened body between the case of the impregnation treatment given to the surface of the mortar hardened body with the solution containing the sodium sulfate and that of no impregnation treatment and/or the impregnation treatment with water, it is confirmed by the experiment 2-2 that there is no remarkable difference in the effect, as compared with the impregnation treatment with water, and therefore, it is guessed that use of the sodium sulfate singly is less effective in reducing the drying shrinkage.

(166) (Experiment 2-2)

(167) An experiment 2-2 was conducted to confirm the presence/absence of the effects resulting from an impregnation treatment given to a usual mortar hardened body having a water/cement ratio of 60% with water containing sodium sulfate Na.sub.2SO.sub.4 as the sulfate.

(168) (1) Experimental Conditions

(169) Conditions of the experiment are shown on a table 5 below.

(170) TABLE-US-00005 TABLE 5 Target flow value Immersion Immersion (15 times Immersion time date (after w/c s/c of rodding) condition (min) demolding) Symbol 60% 2.4 200 10 (mm) None N Water 1 Third day 3rd-day water Seventh day 7th-day water 10% Na.sub.2SO.sub.4 1 Third day 3rd-day sulfate Seventh day 7th-day sulfate

(171) Wherein

(172) c: Ordinary portland cement

(173) w: Water

(174) s: River sand
Na.sub.2SO.sub.4 concentration=Na.sub.2SO.sub.4(g)/(Na.sub.2SO.sub.4(g)+water(g))=10%

(175) Symbols given to specimens in the table 5 represent the following conditions respectively.

(176) N: No impregnation treatment

(177) 3rd-day water: Immersion of specimen in water for one minute on the third day after demolding

(178) 7th-day water: Immersion of specimen in water for one minute on the seventh day after demolding

(179) 3rd-day sulfate: Immersion of specimen in solution containing Na.sub.2SO.sub.4 at concentration of 10% for one minute on the third day after demolding

(180) 7th-day sulfate: Immersion of specimen in solution containing Na.sub.2SO.sub.4 at concentration of 10% for one minute on the seventh day after demolding

(181) The experiment 2-2 was conducted in the case of a water/cement ratio of 60% to examine whether or not the resultant effects based on sulfate (sodium sulfate Na.sub.2SO.sub.4) are affected by a water immersion treatment given to each specimen every week in the period from the age of 28 days to the age of 91 days (13 weeks).

(182) (Experimental Results)

(183) Results of the experiment are shown in FIG. 10.

(184) FIG. 10 is a graph showing an age (days) after demolding on its horizontal axis and a length change rate (%) on its vertical axis.

(185) A specimen (N) given no impregnation treatment resulted in about a 0.113% reduction in the length by the age of 91 days due to drying shrinkage.

(186) A specimen (3rd-day water) immersed in water for one minute on the third day after demolding resulted in about a 0.085% reduction in the length by the age of 91 days (13 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(187) A specimen (7th-day water) immersed in water for one minute on the seventh day after demolding resulted in about a 0.085% reduction in the length by the age of 91 days (13 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(188) A specimen (3rd-day sulfate) immersed in a solution containing Na.sub.2SO.sub.4 at a concentration of 10% for one minute on the third day after demolding resulted in about a 0.089% reduction in the length by the age of 91 days (13 weeks), while length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(189) A specimen (7th-day sulfate) immersed in a solution containing Na.sub.2SO.sub.4 at a concentration of 10% for one minute on the seventh day after demolding resulted in about a 0.089% reduction in the length by the age of 91 days (13 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(190) (3) Conclusions

(191) As the result of comparison in drying shrinkage and hardening of the hardened body between the case of the impregnation treatment given to the surface of the mortar hardened body with the solution containing the sodium sulfate and that of no impregnation treatment and/or the impregnation treatment with water, like the experiment 2-1, it is confirmed by the experiment 2-2 that there is no remarkable difference in the effect, as compared with the impregnation treatment with water, and therefore, it is guessed that use of the sodium sulfate singly is less effective in reducing the drying shrinkage.

(192) (Experiment 2-3)

(193) An experiment 2-3 was conducted to confirm the presence/absence of the effects obtained further when changing a sodium sulfate solution immersion time and when changing a sodium sulfate concentration, with reference to the results of the experiments 2-1 and 2-2. It is noted that a mortar hardened body was prepared at a water/cement ratio of 50%.

(194) (1) Experimental Conditions

(195) Conditions of the experiment are shown in a table 6 below.

(196) TABLE-US-00006 TABLE 6 Target flow value Immersion Immersion (15 times Immersion time date (after w/c s/c of rodding) condition (min) demolding) Symbol 50% 1.7 200 10 (mm) None N Water 1 Third day 3rd-day water Seventh day 7th-day water 10 Third day 3rd-day water 10 min Seventh day 7th-day water 10 min 30 Third day 3rd-day water 30 min Seventh day 7th-day water 30 min 5% Na.sub.2SO.sub.4 1 Third day 3rd-day 5%-sulfate Seventh day 7th-day 5%-sulfate 10% Na.sub.2SO.sub.4 1 Third day 3rd-day 10%-sulfate Seventh day 7th-day 10%-sulfate 10 Third day 3rd-day 10%-sulfate 10 min Seventh day 7th-day 10%-sulfate 10 min 30 Third day 3rd-day 50%-sulfate 30 min Seventh day 7th-day 50%-sulfate 30 min

(197) Wherein

(198) c: Ordinary portland cement

(199) w: Water

(200) s: River sand

(201) Symbols given to specimens in the table 6 represent the following conditions respectively.

(202) N: No impregnation treatment

(203) 3rd-day water: Immersion of specimen in water for one minute on the third day after demolding

(204) 7th-day water: Immersion of specimen in water for one minute on the seventh day after demolding

(205) 3rd-day water 10 min: Immersion of specimen in water for 10 minutes on the third day after demolding

(206) 7th-day water 10 min: Immersion of specimen in water for 10 minutes on the seventh day after demolding

(207) 3rd-day water 30 min: Immersion of specimen in water for 30 minutes on the third day after demolding

(208) 7th-day water 30 min: Immersion of specimen in water for 30 minutes on the seventh day after demolding

(209) 3rd-day 5%-sulfate: Immersion of specimen in solution containing Na.sub.2SO.sub.4 at concentration of 5% for one minute on the third day after demolding

(210) 7th-day 5%-sulfate: Immersion of specimen in solution containing Na.sub.2SO.sub.4 at concentration of 5% for one minute on the seventh day after demolding

(211) 3rd-day 10%-sulfate: Immersion of specimen in solution containing Na.sub.2SO.sub.4 at concentration of 10% for one minute on the third day after demolding

(212) 7th-day 10%-sulfate: Immersion of specimen in solution containing Na.sub.2SO.sub.4 at concentration of 10% for one minute on the seventh day after demolding

(213) 3rd-day 10%-sulfate 10 min: Immersion of specimen in solution containing Na.sub.2SO.sub.4 at concentration of 10% for 10 minutes on the third day after demolding

(214) 7th-day 10%-sulfate 10 min: Immersion of specimen in solution containing Na.sub.2SO.sub.4 at concentration of 10% for 10 minutes on the seventh day after demolding

(215) 3rd-day 10%-sulfate 30 min: Immersion of specimen in solution containing Na.sub.2SO.sub.4 at concentration of 10% for 30 minutes on the third day after demolding

(216) 7th-day 10%-sulfate 30 min: Immersion of specimen in solution containing Na.sub.2SO.sub.4 at concentration of 10% for 30 minutes on the seventh day after demolding
Na.sub.2SO.sub.4 concentration=Na.sub.2SO.sub.4 (g)/(Na.sub.2SO.sub.4 (g)+water (g))

(217) (2) Experimental Results

(218) Results of the experiment are shown in FIGS. 11 to 13.

(219) FIG. 11 is a graph showing a relation between an age (days) and a length change rate (%) in the experiment 2-3 when changing a sodium sulfate solution immersion time (3rd-day 10%-sulfate, 3rd-day 10%-sulfate 10 min and 3rd-day 10%-sulfate 30 min), in regard to the case where after an impregnation treatment with sodium sulfate on the third day after demolding, a water immersion treatment was given to each specimen every week in the period from the age of 28 days (4 weeks) to the age of 91 days (13 weeks).

(220) A specimen given no impregnation treatment resulted in about a 0.105% reduction in the length by the age of 91 days due to drying shrinkage.

(221) A specimen (3rd-day water) immersed in water for one minute on the third day after demolding resulted in about a 0.095% reduction in the length by the age of 91 days (13 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(222) A specimen (3rd-day water 10 min) immersed in water for 10 minutes on the third day after demolding resulted in about a 0.093% reduction in the length by the age of 91 days (13 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(223) A specimen (3rd-day water 30 min) immersed in water for 30 minutes on the third day after demolding resulted in about a 0.089% reduction in the length by the age of 91 days (13 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(224) A specimen (3rd-day 10%-sulfate) immersed in a solution containing sodium sulfate at a concentration of 10% for one minute on the third day after demolding resulted in about a 0.090% reduction in the length by the age of 91 days (13 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(225) A specimen (3rd-day 10%-sulfate 10 min) immersed in a solution containing sodium sulfate at a concentration of 10% for 10 minutes on the third day after demolding resulted in about a 0.095% reduction in the length by the age of 91 days (13 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(226) A specimen (3rd-day 10%-sulfate 30 min) immersed in a solution containing sodium sulfate at a concentration of 10% for 30 minutes on the third day after demolding resulted in about a 0.098% reduction in the length by the age of 91 days (13 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(227) FIG. 12 is a graph showing a relation between an age (days) and a length change rate (%) in the experiment 2-3 when changing a sodium sulfate concentration (3rd-day 5%-sulfate, 7th-day 5%-sulfate, 3rd-day 10%-sulfate and 7th-day 10%-sulfate).

(228) A specimen (N) given no impregnation treatment resulted in about a 0.105% reduction in the length by the age of 91 days due to drying shrinkage, as shown also in FIG. 11.

(229) A specimen (3rd-day 5%-sulfate) immersed in a solution containing sodium sulfate at a concentration of 5% for one minute on the third day after demolding resulted in about a 0.098% reduction in the length by the age of 91 days (13 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(230) A specimen (7th-day 5%-sulfate) immersed in a solution containing sodium sulfate at a concentration of 5% for one minute on the seventh day after demolding resulted in about a 0.115% reduction in the length by the age of 91 days (13 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(231) A specimen (3rd-day 10%-sulfate) immersed in a solution containing sodium sulfate at a concentration of 10% for one minute on the third day after demolding resulted in about a 0.090% reduction in the length by the age of 91 days (13 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(232) A specimen (7th-day 10%-sulfate) immersed in a solution containing sodium sulfate at a concentration of 10% for one minute on the seventh day after demolding resulted in about a 0.095% reduction in the length by the age of 91 days (13 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(233) FIG. 13 is a graph showing a relation between an age (days) and a length change rate (%) in the experiment 2-3 when changing a sodium sulfate solution immersion time (7th-day 10%-sulfate, 7th-day 10%-sulfate 10 min and 7th-day 10%-sulfate 30 min), in regard to the case where after an impregnation treatment with sodium sulfate on the seventh day after demolding, each specimen was given a water immersion treatment every week in the period from the age of 28 days (4 weeks) to the age of 91 days (13 weeks).

(234) A specimen (N) given no impregnation treatment resulted in about a 0.105% reduction in the length by the age of 91 days due to drying shrinkage, as shown also in FIGS. 11 and 12.

(235) A specimen (7th-day water) immersed in water for one minute on the seventh day after demolding resulted in about a 0.093% reduction in the length by the age of 91 days (13 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks),

(236) A specimen (7th-day water 10 min) immersed in water for 10 minutes on the seventh day after demolding resulted in about a 0.102% reduction in the length by the age of 91 days (13 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(237) A specimen (7th-day water 30 min) immersed in water for 30 minutes on the seventh day after demolding resulted in about a 0.086% reduction in the length by the age of 91 days (13 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(238) A specimen (7th-day 10%-sulfate) immersed in a solution containing sodium sulfate at a concentration of 10% for one minute on the seventh day after demolding resulted in about a 0.093% reduction in the length by the age of 91 days (13 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(239) A specimen (7th-day 10%-sulfate 10 min) immersed in a solution containing sodium sulfate at a concentration of 10% for 10 minutes on the seventh day after demolding resulted in about a 0.093% reduction in the length by the age of 91 days (13 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(240) A specimen (7th-day 10%-sulfate 30 min) immersed in a solution containing sodium sulfate at a concentration of 10% for 30 minutes on the seventh day after demolding resulted in about a 0.095% reduction in the length by the age of 91 days (13 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(241) (3) Conclusions

(242) It is confirmed by the experiment 2-3 that a difference appears in the magnitude of drying shrinkage depending on a difference of the sodium sulfate solution immersion time and/or the sodium sulfate concentration, in which case, however, it cannot be said that the impregnation treatment with the sodium sulfate is effective in reducing the drying shrinkage as compared with the impregnation treatment with water, and therefore, it is guessed that use of the sodium sulfate singly is less effective in reducing the drying shrinkage.

Example 2

(243) An example 2 of the present invention will now be described on a drying shrinkage reduction effect resulting from an impregnation treatment given to the surface of a cement-based hardened body after demolding with a solution containing both urea and sulfate (experiments 3-1 to 3-3, 4-1 and 4-2)

(244) (Experiment 3-1)

(245) An experiment 3-1 was conducted to confirm the effects resulting from an impregnation treatment given to a usual mortar hardened body having a water/cement ratio of 40% with water (a mixture of solution containing urea at a concentration of 50% and solution containing sodium sulfate at a concentration of 10%) containing both urea and sodium sulfate Na.sub.2SO.sub.4 which is a type of metal sulfate.

(246) (1) Experimental Conditions

(247) Conditions of the experiment are shown on a table 7 below.

(248) TABLE-US-00007 TABLE 7 Target flow value Immersion Immersion (15 times Immersion time date (after w/c s/c of rodding) condition (min) demolding) Symbol 40% 1.2 200 10 (mm) None N Water 1 Third day 3rd-day water Seventh day 7th-day water mix 1 Third day 3rd-day mix Seventh day 7th-day mix

(249) Wherein

(250) c: Ordinary portland cement

(251) w: Water

(252) s: River sand

(253) mix: [sodium sulfate:water:urea=1:9:10 (mass)]

(254) Symbols given to specimens in the table 7 represent the following conditions respectively.

(255) N: No impregnation treatment

(256) 3rd-day water: Immersion of specimen in water for one minute on the third day after demolding

(257) 7th-day water: Immersion of specimen in water for one minute on the seventh day after demolding

(258) 3rd-day mix: Immersion of specimen in solution containing both urea and sodium sulfate for one minute on the third day after demolding

(259) 7th-day mix: Immersion of specimen in solution containing both urea and sodium sulfate for one minute on the seventh day after demolding

(260) The experiment 3-1 was conducted also to examine whether or not the resultant effects are affected by a water immersion treatment given to each specimen every week in the period from the age of 28 days (4 weeks) to the age of 77 days (11 weeks).

(261) (2) Experimental Results

(262) Results of the experiment are shown in FIG. 14.

(263) FIG. 14 is a graph showing an age (days) after demolding on its horizontal axis and a length change rate (%) at its vertical axis.

(264) A specimen (N) given no impregnation treatment resulted in about a 0.090% reduction in the length by the age of 48 days due to drying shrinkage, and afterwards, the length thereof was maintained approximately constant.

(265) A specimen (3rd-day water) immersed in water for one minute on the third day after demolding resulted in about a 0.082% reduction in the length by the age of 77 days (11 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(266) A specimen (7th-day water) immersed in water for one minute on the seventh day after demolding resulted in about a 0.084% reduction in the length by the age of 77 days (11 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(267) A specimen (3rd-day mix) immersed in a mixture of urea solution and sodium sulfate solution for one minute on the third day after demolding resulted in about a 0.072% reduction in the length by the age of 77 days (11 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(268) A specimen (7th-day mix) immersed in a mixture of urea solution and sodium sulfate solution for one minute on the seventh day after demolding resulted in about a 0.070% reduction in the length by the age of 77 days (11 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(269) (3) Conclusions

(270) It is confirmed by the experiment 3-1 that the impregnation treatment given to the surface of the mortar hardened body with the mixture prepared by dissolving both urea and sodium sulfate in water allows about a 15 to 20% reduction in the drying shrinkage of the hardened body to be obtained at the point of the age of 77 days (11 weeks), as compared with the case of no impregnation treatment and/or the impregnation treatment with water.

(271) It is also confirmed that in the process of the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks), the drying shrinkage reduction effect is maintained, and further, in regard to the comparison with the experiment 1-1 conducted on condition of using the solution containing only the urea, any reduction in the drying shrinkage reduction effect due to the water immersion treatment is not found, unlike the experiment 1-1. Therefore, use of the mixture of urea solution and sodium sulfate solution allows expectation for continuance of the drying shrinkage reduction effect even for exterior structures or like structures exposed to wind and rain.

(272) (Experiment 3-2)

(273) An experiment 3-2 was conducted to confirm the effects resulting from an impregnation treatment given to a usual mortar hardened body having a water/cement ratio of 60% with water containing both urea and sodium sulfate Na.sub.2SO.sub.4 as the sulfate.

(274) (1) Experimental Conditions

(275) Conditions of the experiment are shown on a table 8 below.

(276) TABLE-US-00008 TABLE 8 Target flow value Immersion Immersion (15 times Immersion time date (after w/c s/c of rodding) condition (min) demolding) Symbol 60% 2.4 200 10 (mm) None N Water 1 Third day 3rd-day water Seventh day 7th-day water mix 1 Third day 3rd-day mix Seventh day 7th-day mix

(277) Wherein

(278) c: Ordinary portland cement

(279) w: Water

(280) s: River sand

(281) mix: [sodium sulfate:water:urea=1:9:10 (mass)]

(282) Symbols given to specimens in the table 8 represent the following conditions respectively.

(283) N: No impregnation treatment

(284) 3rd-day water: Immersion of specimen in water for one minute on the third day after demolding

(285) 7th-day water: Immersion of specimen in water for one minute on the seventh day after demolding

(286) 3rd-day mix: Immersion of specimen in solution containing both urea and sodium sulfate for one minute on the third day after demolding

(287) 7th-day mix: Immersion of specimen in solution containing both urea and sodium sulfate for one minute on the seventh day after demolding

(288) The experiment 3-1 was conducted also to examine whether or not the resultant effects are affected by a water immersion treatment given to each specimen every week in the period from the age of 28 days (4 weeks) to the age of 77 days (11 weeks).

(289) (2) Experimental Results

(290) Results of the experiment are shown in FIG. 15.

(291) FIG. 15 is a graph showing an age (days) after demolding on its horizontal axis and a length change rate (%) on its vertical axis.

(292) A specimen (N) given no impregnation treatment resulted in about a 0.079% reduction in the length by the age of 42 days due to drying shrinkage, and afterwards, the length thereof was maintained approximately constant.

(293) A specimen (3rd-day water) immersed in water for one minute on the third day after demolding resulted in about a 0.068% reduction in the length by the age of 77 days (11 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(294) A specimen (7th-day water) immersed in water for one minute on the seventh day after demolding resulted in about a 0.070% reduction in the length by the age of 77 days (11 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(295) A specimen (3rd-day mix) immersed in a mixture of urea solution and sodium sulfate solution for one minute on the third day after demolding resulted in about a 0.050% reduction in the length by the age of 77 days (11 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(296) A specimen (7th-day mix) immersed in a mixture of urea solution and sodium sulfate solution for one minute on the seventh day after demolding resulted in about a 0.052% reduction in the length by the age of 77 days (11 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(297) (3) Conclusions

(298) It is confirmed by the experiment 3-2 that the impregnation treatment given to the surface of the mortar hardened body with the mixture prepared by dissolving both urea and sodium sulfate in water allows about a 15 to 35% reduction in the drying shrinkage of the hardened body to be obtained at the point of the age of 77 days (11 weeks), as compared with the case of no impregnation treatment and/or the impregnation treatment with water.

(299) It is also confirmed that the drying shrinkage reduction effect is maintained even under repeated wetting and drying conditions resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks). Therefore, use of the mixture of urea solution and sodium sulfate solution allows expectation for continuance of the drying shrinkage reduction effect even for exterior structures or like structures exposed to wind and rain.

(300) (Experiment 3-3)

(301) An experiment 3-3 was conducted to confirm the presence/absence of the effects obtained when changing a mixture immersion time, with reference to the results of the experiments 3-1 and 3-2. It is noted that a mortar hardened body was prepared at the water/cement ratio of 50%.

(302) (1) Experimental Conditions

(303) Conditions of the experiment are shown on a table 9 below.

(304) TABLE-US-00009 TABLE 9 Target flow value Immersion Immersion (15 times Immersion time date (after w/c s/c of rodding) condition (min) demolding) Symbol 50% 1.7 200 10 (mm) None N Water 1 Third day 3rd-day water Seventh day 7th-day water 10 Third day 3rd-day 10 min Seventh day 7th-day 10 min 30 Third day 3rd-day 30 min Seventh day 7th-day 30 min mix 1 Third day 3rd-day mix Seventh day 7th-day mix 10 Third day 3rd-day mix 10 min Seventh day 7th-day mix 10 min 30 Third day 3rd-day mix 30 min Seventh day 7th-day mix 30 min

(305) Wherein

(306) c: Ordinary portland cement

(307) w: Water

(308) s: River sand

(309) mix: [sodium sulfate:water:urea=1:9:10 (mass)]

(310) Symbols given to specimens in the table 9 represent the following conditions respectively.

(311) N: No impregnation treatment

(312) 3rd-day water: Immersion of specimen in water for one minute on the third day after demolding

(313) 7th-day water: Immersion of specimen in water for one minute on the seventh day after demolding

(314) 3rd-day water 10 min: Immersion of specimen in water for 10 minutes on the third day after demolding

(315) 7th-day water 10 min: Immersion of specimen in water for 10 minutes on the seventh day after demolding

(316) 3rd-day water 30 min: Immersion of specimen in water for 30 minutes on the third day after demolding

(317) 7th-day water 30 min: Immersion of specimen in water for 30 minutes on the seventh day after demolding

(318) 3rd-day mix: Immersion of specimen in solution containing both urea and sodium sulfate for one minute on the third day after demolding

(319) 7th-day mix: Immersion of specimen in solution containing both urea and sodium sulfate for one minute on the seventh day after demolding

(320) 3rd-day mix 10 min: Immersion of specimen in solution containing both urea and sodium sulfate for 10 minutes on the third day after demolding

(321) 7th-day mix 10 min: Immersion of specimen in solution containing both urea and sodium sulfate for 10 minutes on the seventh day after demolding

(322) 3rd-day mix 30 min: Immersion of specimen in solution containing both urea and sodium sulfate for 30 minutes on the third day after demolding

(323) 7th-day mix 30 min: Immersion of specimen in solution containing both urea and sodium sulfate for 30 minutes on the seventh day after demolding

(324) The experiment 3-3 was conducted also to examine whether or not the resultant effects are affected by a water immersion treatment given to each specimen every week in the period from the age of 28 days (4 weeks) to the age of 77 days (11 weeks).

(325) (2) Experimental Results

(326) Results of the experiment are shown in FIGS. 16 and 17.

(327) FIG. 16 is a graph showing a relation between an age (days) and a length change rate (%) in the experiment 3-3 when changing a mixture immersion time (3rd-day mix, 3rd-day mix 10 min, and 3rd-day mix 30 min), in regard to the case where after an impregnation treatment with the mixture prepared by dissolving both urea and sodium sulfate in water on the third day after demolding, each specimen was given a water immersion treatment every week in the period from the age of 28 days (4 weeks) to the age of 91 days (13 weeks).

(328) A specimen (N) given no impregnation treatment resulted in about a 0.086% reduction in the length by the age of 48 days due to drying shrinkage, and afterwards, the length thereof was maintained approximately constant.

(329) A specimen (3rd-day water) immersed in water for one minute on the third day after demolding resulted in about a 0.077% reduction in the length by the age of 77 days (11 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(330) A specimen (3rd-day water 10 min) immersed in water for 10 minutes on the third day after demolding resulted in about a 0.073% reduction in the length by the age of 77 days (11 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(331) A specimen (3rd-day water 30 mn) immersed in water for 30 minutes on the third day after demolding resulted in about a 0.073% reduction in the length by the age of 77 days (11 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(332) A specimen (3rd-day mix) immersed in a mixture of urea solution and sodium sulfate solution for one minute on the third day after demolding resulted in about a 0.053% reduction in the length by the age of 77 days (11 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(333) A specimen (3rd-day mix 10 min) immersed in a mixture of urea solution and sodium sulfate solution for 10 minutes on the third day after demolding resulted in about a 0.046% reduction in the length by the age of 77 days (11 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(334) A specimen (3rd-day mix 30 min) immersed in a mixture of urea solution and sodium sulfate solution for 30 minutes on the third day after demolding resulted in about a 0.048% reduction in the length by the age of 77 days (11 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(335) FIG. 17 is a graph showing a relation between an age (days) and a length change rate (%) in the experiment 3-3 when changing a mixture immersion time (7th-day mix, 7th-day mix 10 min and 7th-day mix 30 min), in regard to the case where after an impregnation treatment with a mixture prepared by dissolving both urea and sodium sulfate in water on the seventh day after demolding, each specimen was given a water immersion treatment every week in the period from the age of 28 days (4 weeks) to the age of 91 days (13 weeks).

(336) A specimen (N) given no impregnation treatment resulted in about a 0.086% reduction in the length by the age of 48 days due to drying shrinkage, and afterwards, the length thereof was maintained approximately constant.

(337) A specimen (7th-day water) immersed in water for one minute on the seventh day after demolding resulted in about a 0.072% reduction in the length by the age of 77 days (11 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(338) A specimen (7th-day water 10 min) immersed in water for 10 minutes on the seventh day after demolding resulted in about a 0.072% reduction in the length by the age of 77 days (11 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(339) A specimen (7th-day water 30 min) immersed in water for 30 minutes on the seventh day after demolding resulted in about a 0.066% reduction in the length by the age of 77 days (11 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(340) A specimen (7th-day mix) immersed in a mixture of urea solution and sodium sulfate solution for one minute on the seventh day after demolding resulted in about a 0.058% reduction in the length by the age of 77 days (11 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(341) A specimen (7th-day mix 10 min) immersed in a mixture of urea solution and sodium sulfate solution for 10 minutes on the seventh day after demolding resulted in about a 0.048% reduction in the length by the age of 77 days (11 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(342) A specimen (7th-day mix 30 min) immersed in a mixture of urea solution and sodium sulfate solution for 30 minutes on the seventh day after demolding resulted in about a 0.039% reduction in the length by the age of 77 days (11 weeks), with length change rate fluctuations resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks).

(343) (3) Conclusions

(344) It is confirmed by the experiment 3-3 that the impregnation treatment given to the surface of the mortar hardened body with the mixture prepared by dissolving both urea and sodium sulfate in water allows about a 30 to 40% reduction in the drying shrinkage of the hardened body to be obtained at the point of the age of 77 days (11 weeks), as compared with the case of no impregnation treatment and/or the impregnation treatment with water.

(345) It is also confirmed that the drying shrinkage reduction effect is maintained even in repeated wetting and drying conditions resulting from the water immersion treatment given to each specimen every week after the age of 28 days (4 weeks). Therefore, use of the mixture of urea solution and sodium sulfate solution allows expectation for continuance of the drying shrinkage reduction effect even for exterior structures or like structures exposed to wind and rain.

(346) For the immersion treatment given to the specimen in the mixture of urea solution and sodium sulfate solution on the seventh day after demolding, it is found that as the immersion time becomes longer in the order of one minute, 10 minutes and 30 minutes, a greater drying shrinkage reduction effect is obtained, while for the immersion treatment given to the specimen in the mixture of urea solution and sodium sulfate solution on the third day after demolding, there is no clear difference in the drying shrinkage reduction effect between the condition of the immersion time of 10 min and that of the immersion time of 30 min at the point of the age of 77 days.

(347) (Experiment 4-1)

(348) The experiments 1-1 to 1-3 in the example 1 and the experiments 3-1 to 3-3 in the example 2 were for the mortar hardened body, whereas an experiment 4-1 was conducted on a concrete hardened body having a water/cement ratio of 40%.

(349) (1) Experimental Conditions

(350) Conditions of the experiment are shown on a table 10 below.

(351) TABLE-US-00010 TABLE 10 Target Target air- Immersion Immersion slump content Immersion time date (after w/c s/a sp/c value value condition (min) demolding) Symbol 40% 42.7% 0.12% 7 0.5 (cm) 4.5% None N Water 1 Third day 3rd-day water Urea 1 Third day 7th-day urea mix 1 Third day 3rd-day mix

(352) Wherein

(353) c: Ordinary portland cement

(354) w: Water

(355) s: River sand

(356) a: River sand+gravels of No. 6 type

(357) sp: High-performance AE water-reducing agent
Urea concentration=urea(g)/(urea(g)+water(g))=50%

(358) mix: [sodium sulfate:water:urea=1:9:10 (mass)]

(359) Symbols given to specimens in the table 10 represent the following conditions respectively.

(360) N: No impregnation treatment

(361) 3rd-day water: Immersion of specimen in water for one minute on the third day after demolding

(362) 3rd-day urea: Immersion of specimen in solution containing urea at concentration of 50% for one minute on the third day after demolding

(363) 3rd-day mix: Immersion of specimen in solution containing both urea and sodium sulfate for one minute on the third day after demolding

(364) (2) Experimental Results

(365) Results of the experiment are shown in FIG. 18.

(366) FIG. 18 is a graph showing an age (days) on its horizontal axis and a length change rate (%) on its vertical axis.

(367) At the point of the age of 56 days (8 weeks), the specimen (3rd-day water) immersed in water for one minute on the third day after demolding had almost the same drying shrinkage reduction effect as the specimen (N) given no impregnation treatment, while the specimen (3rd-day urea) immersed in the solution containing urea for one minute on the third day after demolding resulted in about a 10% reduction in the length change rate, and thus, the drying shrinkage reduction effect was found.

(368) The specimen (3rd-day mix) immersed in the solution containing both urea and sodium sulfate for one minute on the third day after demolding had a smaller length change rate until the age of 42 days (6 weeks) as compared with the specimen (3rd-day urea) immersed in the solution containing urea for one minute on the third day after demolding, and afterwards, came to have almost the same length change rate as the specimen (3rd-day urea) at the age of 56 days (8 weeks), and further, about a 8% reduction in the length change rate was found, in contrast to the specimen N given no impregnation treatment.

(369) (3) Conclusions

(370) It is confirmed by the experiment 4-1 conducted on the concrete that the effects resulting from the impregnation treatment with the solution prepared by dissolving urea or both urea and sodium sulfate in water are relatively small, as compared with the experiments conducted on the mortar, in which case, however, since the concrete is innately smaller than the mortar in the length change rate itself, it is found that there is the drying shrinkage reduction effect even in the concrete as well.

(371) (Experiment 4-2)

(372) An experiment 4-2 was conducted on a concrete hardened body having a water/cement ratio of 60%, like the experiment 4-1.

(373) (1) Experimental Conditions

(374) Conditions of the experiment are shown on a table 11 below.

(375) TABLE-US-00011 TABLE 11 Target Target air- Immersion Immersion slump content Immersion time date (after w/c s/a sp/c value value condition (min) demolding) Symbol 60% 49.0% 0.10% 8.5 0.5 (cm) 5.5% None N Water 1 Third day 3rd-day water Urea 1 Third day 7th-day urea mix 1 Third day 3rd-day mix

(376) Wherein

(377) c: Ordinary portland cement

(378) w: Water

(379) s: River sand

(380) a: River sand+gravels of No. 6 type

(381) sp: High-performance AE water-reducing agent
Urea concentration=urea(g)/(urea(g)+water(g))=50%

(382) mix: [sodium sulfate:water:urea=1:9:10 (mass)]

(383) Symbols given to specimens in the table 11 represent the following conditions respectively.

(384) N: No impregnation treatment

(385) 3rd-day water: Immersion of specimen in water for one minute on the third day after demolding

(386) 3rd-day urea: Immersion of specimen in solution containing urea at concentration of 50% for one minute on the third day after demolding

(387) 3rd-day mix: Immersion of specimen in solution containing both urea and sodium sulfate for one minute on the third day after demolding

(388) (2) Experimental Results

(389) Results of the experiment are shown in FIG. 19.

(390) FIG. 19 is a graph showing an age (days) on its horizontal axis and a length change rate (%) on its vertical axis.

(391) At the point of the age of 56 days (8 weeks), the specimen (3rd-day water) immersed in water for one minute on the third day after demolding had almost the same drying shrinkage reduction effect as the specimen (N) given no impregnation treatment, while the specimen (3rd-day urea) immersed in the solution containing urea for one minute on the third day after demolding resulted in about a 11% reduction in the length change rate, and thus, the drying shrinkage reduction effect was found.

(392) The specimen (3rd-day mix) immersed in the solution containing both urea and sodium sulfate for one minute on the third day after demolding had a smaller length change rate until the age of 42 days (6 weeks) as compared with the specimen (3rd-day urea) immersed in the solution containing urea for one minute on the third day after demolding, and afterwards, came to have almost the same length change rate as the specimen (3rd-day urea) at the age of 56 days (8 weeks), and further, about a 9% reduction in the length change rate was found, in contrast to the specimen (N) given no impregnation treatment.

(393) (3) Conclusions

(394) It is confirmed by the experiment 4-2 conducted on the concrete that there is a tendency approximately similar to that shown in the experiment 4-1 conducted on the concrete, while an innate length change rate itself of the concrete specimen is somewhat increased, as compared with the experiment 4-1 on the higher quality concrete with the water/cement ratio of 40%.