FR2774982A1 - Cementitious composition with accelerated initial and final set time and increased average rate of heat evolution - Google Patents

Abstract

The composition comprises an admixture of aluminium oxide, silicon dioxide and zirconium oxide. Preferably the composition contains 70-96 wt.% aluminium oxide, 2-15 wt.% silicon dioxide and 2-15 wt.% zirconium oxide. The composition further contains high alumina cement and/or Portland cement with a plasticising, water reducing and defoaming agent especially a naphthalene sulphonate, melamine sulphonate or lignosulphonate based compound. The composition may also include an air releasing and/or gas generating agent especially fluidised coke and azodicarbonamide. An air-entraining agent, a corrosion inhibitor and a mineral admixture may also be included.

Description

The present invention relates to improvements in

  cement-based compositions and in particular

  the use of an additive in such compositions.

  The term "cement-based compositions" as used herein means compositions which set and harden by chemical interaction with water and which are also capable of it in the presence of water. These compositions include water-repellent, decorative, protective cement coatings, etc., as well as mixtures with aggregates and water such as concrete, mortar, grout.

  cement, and products made therefrom.

  In the construction industry, and in particular

  Especially in the repair of concrete structures such as roads and walls and construction platforms, and in the filling of voids and holes to form props or stable foundations for heavy machinery or equipment, we needed cement-based compositions which set in a hard mass having sufficient initial strength to withstand the stresses and loads applied, and which reach this state in an abridged period of time and with an increased rate of heat release. There have been many attempts in the past to formulate additives for cementitious compositions having these characteristics, but these attempts have met with only limited success. Additives

  used often gave properties and side effects

  undesirable, for example corrosion of the reinforcing steel incorporated in the concrete by additives containing chloride, an insufficient gain of initial resistance and a degradation of the resistance in the long term. Most of the additives developed for alumina-rich cements were ineffective in Portland cements, while the additives produced for Portland cement were not

  satisfactory for cements rich in alumina. 35 Examples of previous attempts to produce

  tion of satisfactory additives are described by M. Shimizu, T. Tano, K. Uchida and N. Kitaoka "Concrete Additive" - Japan Kokai 79 50528, April 20, 1979; Chem. Abstr., 91 128011 (1979); and by V.I. Remiznikova, T.I. Astrova, V.P. Schmidt,

  M.S. Nizamov, V.N. Popko, V.P. Zuey, M.A. Loginov and A.V.

  Beinarovich "Complex Additive for a Cement-Concrete Mixture" - U.R.S.S. 697,436, November 15, 1979; Chem. Abstr.,

9281279 (1980).

  Thus, an object of the present invention is to provide a cement-based composition comprising an additive which, when mixed with water, sets in an abridged period of time by giving a mass

  hard whose initial resistance is increased.

  Another object of the present invention is to provide a cement-based composition comprising an additive which, when mixed with water, sets in an abridged period of time giving a hard mass whose initial resistance is which is more

  high average speed of heat generation.

  Another object of the present invention is to provide a cement-based composition comprising an additive which, when mixed with water, sets in a period

  of shortened time by giving a hard mass whose resistance

  initial tance is increased, and which has a higher average rate of heat release and includes an agent

  plasticizer (reducing water content) and defoamer.

  Yet another object of the present invention is to provide a cement-based composition comprising an additive which, when mixed with water, sets in an abridged period of time giving a hard mass whose initial resistance is increased, and which has a higher average rate of heat release and

  contains an air releasing agent and / or gas generator.

  Yet another object of the present invention is to provide a cement-based composition comprising an additive which, when mixed with water, sets in an abridged period of time giving a hard mass whose initial resistance is increased, and which has a higher average rate of heat release and

  contains an air entraining agent.

  Yet another object of the present invention is to provide a cement-based composition comprising an additive which, when mixed with water, sets in an abridged period of time giving a hard mass whose initial resistance is increased, and has a higher average rate of heat release

  and contains a corrosion inhibitor.

  Yet another object of the present invention is to provide a cement-based composition comprising an additive which, when mixed with water, sets in an abridged period of time giving a hard mass whose initial resistance is increased, and has a higher average rate of heat release

and contains a mineral additive.

  The above objects are achieved according to the present invention by the discovery of a new additive which consists of a combination of aluminum oxide, silicon dioxide and zirconium oxide in the proportions specified below. In addition to the additive, the cementitious composition contains sand and water,

  high alumina or Portland cement content, or a combination

  tion of alumina-rich cement and Portland cement. Plasticizers and defoamers, air releasing agents and / or gas generators, air entraining agents, corrosion inhibitors and mineral additives can also be used with the compositions based on

  cement of the present invention.

  The proportion of aluminum oxide used in the additive of the present invention is from 70 to 96% by weight of the total additive, the proportion of silicon dioxide is from 2 to 15% by weight of the total additive and the proportion of zirconium oxide is 2 to 15% by weight of the total additive. The above objects, features and advantages, as well as others, of the invention will best emerge from

  its detailed description which follows. The following embodiments are modes

  preferred embodiments: the cement composition comprises a cement rich in alumina; - The cement composition comprises a Portland cement; the cement composition comprises a cement rich in alumina and a Portland cement; the cement composition also comprises a plasticizing agent, reducing the water and anti-foam content

  such as, for example, a naphthalene compound-

  sulfonate, melamine sulfonate or lignosulfonate; - The cement composition further comprises an agent releasing air and / or gas generator such as fluidized coke; - The cement composition further comprises a gas generating agent such as azodicarbonamide; - The cement composition further comprises an air entraining agent such as a vinsol resin; - The cement composition further comprises a corrosion inhibitor such as sodium nitrite; - the cement composition also comprises an additive

  mineral such as fly ash.

  According to another of its aspects, the invention relates to a method for shortening the setting time, increasing the initial compressive strength and increasing the average speed of heat release from a cement-based system, characterized in that it consists in adding to the system an additive comprising aluminum oxide, silicon dioxide and zirconium oxide. Preferably, the added aluminum oxide is present in a proportion of 70 to 96% by weight of the additive, the added silicon dioxide is present in a proportion of 2 to 15% by weight of the additive and the added zirconium oxide is present in a proportion of 2 to 15%

by weight of the additive.

  Vinsol resins are obtained by neutralization, using sodium hydroxide, of the insoluble residues remaining after distillation and extraction of pine stumps. These residues are in particular made up of phenolic derivatives

and carboxylic acids.

  These resins which are marketed are described

  in the "Concrete Admixtures Handbook", second edition.

  The invention is further illustrated by the experiments

  following experiences and the results of the experiments presented

  in the Tables below. In the following description,

  percentages are expressed by weight, unless stated

  opposite. In each control sample and each experiment

  rience described below, the water is mixed with the dry mixture and the results are then noted. In all the

  control samples and all experiments except

  tion of experiments 16 and 17, the water content of the

  composition represents 20% of the weight of the dry matter.

  Control sample for Experiments 1, 2 and 3 The same control sample is used for Experiments 1, 2 and 3. The control sample consists of a cement mixture rich in alumina Secar 51, sold by

  Lafarge Calcium Aluminates, Inc., with sand and water.

  The dry mixture of the control sample contains parts

  of cement rich in Secar 51 alumina and sand.

  Experiment 1 In Experiment 1, the percentage of cement rich in alumina Secar 51 is the same as that of the control sample, that is to say 50%; however, the sand content is lowered to 47.5% and the additive is added in an amount of 2.5% of the total mixture. The additive comprises aluminum oxide, A1203, in a proportion of 2.1% of the total mixture; silicon dioxide, SiO2, in a proportion of 0.22% of the total mixture; and zirconium oxide, ZrO2, in a proportion of 0.18% of the mixture

  total. Compared to the additive, aluminum oxide

  titrate 84% of the additive, silicon dioxide 8.8% of the additive and zirconium oxide 7.2% of the additive. Regarding the results of Experiment 1, the initial and final setting times are reduced comparatively

  to the control sample, the initial resistance to compression

  sion (up to 1 day) is increased compared to the sample

  control tillon, and the exothermic peak and the average speed

  temperature rise are both increased compara-

the control sample.

  Experiment 2 In Experiment 2, the percentage of cement rich in alumina Secar 51 remains at 50% of the dry mixture; however, the sand content is further lowered to 45%. In this experiment, the percentage of the additive is doubled, from 2.5% to 5%, and the proportion of each of the components of the additive - aluminum oxide, silicon dioxide and zirconium oxide - is also doubled. (i.e. the proportion of aluminum oxide is increased to 4.2%, the proportion of silicon dioxide to 0.44% and the proportion

  0.36% zirconium oxide). Regarding the Expe-

  rience 2, we observe that the highest percentage of additive in Experiment 2 reduces the initial and final setting times compared to Experiment 1 and the control sample; increases initial compressive strength (up to 1 day) compared to Experiment 1 and the control sample; and increases both the exothermic peak and the average speed of temperature rise comparatively

  to Experiment 1 and to the control sample.

  Experiment 3 In Experiment 3, the percentage of cement rich in alumina Secar 51 remains at 50% of the dry mixture and the sand content of the dry mixture is lowered to 40%. The percentage of additive is doubled compared to that of Experiment 2, and goes to 10% of the dry mixture, and the proportions of aluminum oxide, silicon dioxide and zirconium oxide

  are also doubled compared to Experiment 2 (i.e.

  i.e. the proportion of aluminum oxide is increased to 8.4%, the proportion of silicon dioxide is increased to 0.88% and the proportion of zirconium oxide is increased to 0.72%). The higher percentage of additive included in the mixture of Experiment 3 further reduces the initial and final setting times compared to previous experiments; increases initial resistance to compression (up to 1 day) compared to previous experiences; and further increases the exothermic peak and the average speed of temperature rise compared to previous experiments. Experiment 4

  Another control sample, similar to the sample

  The previous control sample from Experiments 1 to 3 is prepared for Experiment 4. In this other control sample, the cement rich in fused alumina, sold by Lafarge Calcium Aluminates, Inc., replaces the cement rich in alumina Secar 51. To all in the other respects, the control sample from Experiment 4 is identical to the control sample from Experiments 1, 2 and 3. In Experiment 4, the percentage of cement rich in molten alumina remains at 50% of the dry mixture, but the sand content is lowered from 50%, as in the control sample, to 40%. The same additive is added as for Experiment 3, namely 8.4% aluminum oxide,

  0.88% silicon dioxide and 0.72% zirconium oxide.

  With regard to Experiment 4, the initial and final setting times are both reduced compared to its corresponding control sample; the initial compressive strength (up to 1 day) is increased compared to the control sample, and the exothermic peak and the average rate of temperature rise are both increased compared to the control sample. It is observed that the compressive strength at 6 hours is the same for Experiment 4 and the control sample. One possible explanation is that the accelerating effect of the additive is exerted earlier on molten alumina-rich cement (CRA) than on other cements. It is also possible that

  test results fall within the margin of error experi-

  mental 10% usual for cement-based materials.

Experiment 5

  Another control sample, similar to the samples

  previous control tillons, is prepared for Experiment 5.

  In this experiment, a cement rich in alumina Lumnite, sold by Lehigh Portland Cement Company, is substituted for the cement rich in alumina Secar 51 and the cement rich in

  alumina Fade from the previous control sample. The exchange

  control sample for Experiment 5 is the same as the

  previous control samples in all other respects.

  In Experiment 5, the percentage of cement rich in Lumnite alumina remains at 50% of the dry mixture, but the

  sand content is lowered by 50%, as in the sample

  control tillon, 40%. The same additive is added as in Experiments 3 and 4, namely 8.4% aluminum oxide,

  0.88% silicon dioxide and 0.72% zirconium oxide.

  Regarding Experiment 5, the setting times

  initial and final are reduced compared to its exchange

  corresponding control pin; the initial compressive strength (up to 1 day) is increased compared to the control sample, and the exothermic peak and the average temperature rise speed are both increased

  compared to the control sample.

  The following Table 1 contains the quantitative results.

  tatives of Experiments 1 to 5. "CRA" means "rich cement

alumina ".

TABLE 1

  Experience N0 WITNESS | 1 2 | 3 | WITNESS | 4 | WITNESS | 5

INGREDIENTS,%

  CRA Secar 51 50.0 50.0 50.0 50o, 0 - - -

  CRA Fade - - - - 50.0 50.0 - - CRA Lumnite - - - - - - 50.0 50o, o ASZ Additive, total - 2.5 5.0 10.0 - 10.0 - 10.0 including: A1203 - 2.1 4.2 8.4 - 8, 4 - 8.4 SiO2 - 0.22 0.44 0.88 - 0.88 - 0.88 1 0 ZrO2 - 0.18 0.36 0.72 - 0.72 - 0.72 Sand 50.0 47.5 45.0 40.0 50.0 40.0 50.0 40.0 Mixing water, 20% FOR ALL MIXTURES% by weight of the dry mix

PROPERTIES

  Setting time, min Initial 279 221 166 128 193 145 330 159 Final 336 260 180 150 235 170 375 194 Compressive strength, MPa (psi)

3 h - _ 1.38 20.68 - - - -

(200) (3000)

4 h - - 9.31 40.51 - 26.89 - 19.65

(1,350) (5,875) (3,900) (2,850)

  h - 16.5533.10 41.89 28.27 32.75 - 29.65

  (2,400) (4,800) (6,075) (4,100) (4,750) (4,300)

  6 h 4.48 39.9941.71 42.58 36.89 36.89 - 31.37

  (650) (5800) (6050) (6175) (5350) (5350) (4550)

  1 day 56.3659.71 60.05 62.47 47.40 49.64 48.95 50.85

  (8175) (8660) (8710) (9060) (6875) (7200) (7100) (7375)

  Exothermic peak Temperature, C (F) 103.3 111.1 115.6 119.4 105 116.1 98.3 101.1

  (218) (232) (240) (247) (221) (241) (209) (214)

  Time, min 462 362 314 223 310 215 469 338

Average lifting speed

  temperature, 0.172 0.244 0.300 0.433 0.266 0.439 0.161 0.233 C / min (F / min) (0.31) (0.44) (0.54) (0.78) (0.48) (0.79 ) (0.29) (0.42) Experiment 6 The control sample for Experiment 6 is similar to the previous control samples, but gray Portland cement, type II, sold by Lehigh Portland Cement Company, is substituted for the cements of previous control samples. Gray Portland cement constitutes 50% of the dry mixture and sand constitutes 50% of the dry mixture. The term "Portland cement", as used herein, includes cements normally called "Portland cements" in

  technology, as described in reference ASTM C 150.

  In Experiment 6, the percentage of Portland cement, type II, remains the same at 50% of the dry mixture,

  but the sand content is lowered to 40% of the dry mixture.

  The additive constituting 10% of the dry mixture is added.

  The formulation of the additive is the same as in Experiments 3, 4 and 5, namely aluminum oxide in a proportion of 8.4% of the total mixture, silicon dioxide in a proportion of 0, 88% of the total mixture, zirconium oxide in a proportion of 0.72% of the total mixture. Regarding the results of Experiment 6,

  the initial and final setting times are reduced compared to

  When compared to the control sample, the compressive strength (up to 1 day) is increased compared to the control sample, and the exothermic peak and the average speed

  temperature rise are both increased compara-

the control sample.

  Experiment 7 The control sample of Experiment 7 is identical to the control sample of Experiment 6 and Experiment 7

  is identical to Experiment 6, except that in the sample

  control sample and Experiment 7, Portland cement, type III, sold by Lehigh Portland Cement Company, replaces Portland cement, type II, from Experiment 6. Regarding the results of Experiment 7, the times hold

  initial and final are reduced compared to the sample

  control, the compressive strength at 5, 6, 7 and 8 hours is increased, and the exothermic peak and the average temperature rise speed are both increased

  compared to the control sample.

  The following Table 2 contains the quantitative results.

of Experiments 6 and 7.

TABLE 2

Experience N WITNESS 6 WITNESS 7

INGREDIENTS,%

  Portland cement T-II (Lehigh, gray) 50.0 50.0 -

  Portland cement T-III (Lehigh, white) 50.0 50.0 ASZ additive, total - 10.0 - 10.0 including: A1203 - 8.4 - 8.4 SiO2 - 0.88 - 0.88 ZrO2 - 0.72 - 0.72 Sand 50.0 40.0 50, O 40, 0 Mixing water, 20 2 FOR ALL MIXTURES% by weight of the dry mixture

PROPERTIES

  Setting time, min Initial 205 191 147 120 Final 355 271 202 175 Compressive strength, MPa (psi) h - - - 2.24 (325) 6 h - 1.21 1.55 4.31

(175) (225) (625)

7 h 0.69-0.86 1.90 3.45 7.76

(100-125) (275) (500) (1125)

8 h 1.38 2.93 5.00 13.44

(200) (425) (725) (1950)

1 day 24.13 27.58 31.37 39.65

(3,500) (4,000) (4,550) (5,750)

  Exothermic peak Temperature, C (F) 45 54.4 66.1 73.3

(113) (130) (151) (164)

  Time, min 570 480 438 346 Average temperature rise speed, C / min (F / min) 0.039 0.066 0.01 0.155

(0.07) (0.12) (0.18) (0.28)

  Experiment 8 The control sample of Experiment 8 is prepared by mixing the cement rich in alumina Secar 51 in a proportion of 37.5% of the dry mixture, the gray Portland cement, type II, in a proportion of 12.5%. dry mix and sand in a proportion of 50% of the dry mix. In Experiment 8, the percentage of cement rich in alumina Secar 51 and that of Portland cement, type II, remains the same as for the control sample, but the sand content 5 is lowered to 45% and supplemented by additive in the same percentages as for Experiment 2, namely the oxide

  aluminum in a proportion of 4.2% of the dry mixture, silicon dioxide in a proportion of 0.44% of the dry mixture and zirconium oxide in a proportion of 0.36% of the dry mixture. Regarding the results of the Expe-

  rience 8, the initial and final setting times are reduced compared to the control sample, the compressive strength at 2, 3 and 6 hours is increased compared to the control sample, and the exothermic peak and the average speed of temperature rise are both increased

  compared to the control sample.

Experiment 9

  The control sample for Experiment 9 is the same as the control sample for Experiment 8. In Experiment

  rience 9, the percentage of cement rich in Alumina Secar 51 and that of Portland cement, type II, remains the same as for the control sample, but the sand content is lowered to 40% and supplemented by the additive consisting aluminum oxide in a proportion of 8.4% of the dry mixture, silicon dioxide in a proportion of 0.88% of the dry mixture and zirconium oxide in a proportion of 0.72% of the dry mixture. Regarding the results of Experiment 9, the initial and final setting times are

  compared to the control sample, the compressive strength at 2, 3 and 6 hours is increased compared to

  relative to the control sample, and the exothermic peak and the average rate of temperature rise are all

  two increased compared to the control sample.

  The following Table 3 contains the quantitative results.

Experiments 8 and 9.

TABLE 3

Experience N WITNESS 8 9

INGREDIENTS,%

  CRA Secar 51 37.5 37.5 37.5 Portland T-II 12.5 12.5 12.5 Additive ASZ, total - 5.0 10.0 including: A1203 - 4.2 8.4 SiO2 - 0, 44 0.88 ZrO2 - 0.36 0.72 Sand 50.0 45.0 40.0 Mixing water, 20% FOR ALL MIXTURES% by weight of the dry mixture

PROPERTIES

  Setting time, min Initial 127 82 71 Final 150 87 81 Compressive strength, MPa (psi) 2 h - 6.55 11.38

(950) (1650)

3 h 5.52 26.89 27.58

(800) (3900) (4000)

6 h 31.37 32.23 35.51

(4,550) (4,675) (5,150)

  Exothermic peak Temperature, C (F) 104.4 105 106, 1

(220) (221) (223)

  Time, min 230 164 171 Average temperature rise speed, C / min (F / min) 0.355 0.505 0.489

(0.64) (0.91) (0.88)

  Experiments 10 to 15 General Experiments 10 to 15 were designed to determine the limits of each of the compounds used in the additive. Thus, aluminum oxide, silicon dioxide and zirconium oxide were each examined separately in a cement-based composition comprising

  Secar 51 alumina-rich cement, sand and water.

  The same control sample is used for Experiments 15. The control sample consists of a mixture of cement rich in Alumina Secar 51 with sand. The dry mixture of the control sample includes equal parts5 of Secar 51 alumina-rich cement and sand. The water content of the composition is 20% of the weight of the dry matter. Experiment 10 In Experiment 10, the percentage of cement rich in alumina Secar 51 remains identical to that of the control sample, ie 50%; however, the sand content is lowered to 46.5% and aluminum oxide is added in a proportion of 3.5% of the total mixture. The proportion of aluminum oxide, 3.5% of the total mixture, is chosen assuming that the total additive (containing aluminum oxide, silicon dioxide and zirconium oxide) constitutes% of the mixture total dry, and that the proportion of aluminum oxide in the additive is 70%. Thus, aluminum oxide represents 70% of the 5% of total dry additive, or 3.5%. No silicon dioxide or zirconium oxide is added to the mixture. Regarding the results of Experiment 10, the initial and final setting times are reduced compared to the control sample, the resistance to initial compression (up to 1 day) and to 7 days are increased compared to l control sample, and the exothermic peak and the average speed

  temperature rise are both increased compara-

the control sample.

  Experiment 11 In Experiment 11, the percentage of cement rich in alumina Secar 51 remains the same as for the control sample, that is to say 50%; however, the sand content is lowered to 40.4% and aluminum oxide is added in a proportion of 9.6% of the total mixture. The proportion of aluminum oxide, 9.6% of the total mixture, is chosen assuming that the total additive (containing aluminum oxide, silicon dioxide and zirconium oxide) constitutes% of the mixture total dry and that the proportion of aluminum oxide in the additive is 96%. Thus, aluminum oxide represents 9.6% of the total dry mixture. We do not add silicon dioxide or zirconium oxide

  to the mixture. Regarding the results of the Expe-

  rience 11, the initial and final setting times are reduced compared to the control sample and in Experiment 10, the resistance to initial compression (up to 1 day) and to 7 days are increased compared to the control sample , and the exothermic peak and the average speed

  temperature rise are both increased compared to

  ratified to the control sample and to Experiment 10.

  The compressive strength of Experiment 11, compared to Experiment 10, is higher after 4 and 6 hours, but lower after 5, 7 and 8 hours and 1 and

7 days.

  Experiment 12 In Experiment 12, the percentage of cement rich in Secar 51 alumina remains the same as for the control sample, ie 50%; however, the sand content is lowered to 49.9% and silicon dioxide is added in an amount of 0.1% of the total mixture. The proportion of silicon dioxide, 0.1% of the total mixture, is chosen assuming that the total additive (containing aluminum oxide, silicon dioxide and zirconium oxide) constitutes 5% of the total dry mixture and that the proportion of silicon dioxide in the additive is 2%. Thus, silicon dioxide represents 2% of the 5% of the total dry mixture, or 0.1%. No aluminum oxide or zirconium oxide is added to the mixture. Regarding the results of Experiment 12, the initial and final setting times are reduced compared to the control sample but are increased compared to Experiments 10 and 11.35 the resistance to initial compression (up to 1 day ) and at 7 days are increased compared to the control sample, but are reduced compared to Experiments and 11, and the exothermic peak is reduced compared

  to the control sample and to Experiments 10 and 11.

  The average speed of temperature rise is increased compared to the control sample, but decreased

  compared to Experiments 10 and 11.

  Experiment 13 In Experiment 13, the percentage of cement rich in Alumina Secar 51 remains the same as for the control sample, that is to say 50%; however, the sand content is lowered to 48.5% and silicon dioxide is added in an amount of 1.5% of the total mixture. The proportion of silicon dioxide, 1.5% of the total mixture, is chosen

  assuming that the total additive (containing aluminum oxide

  minium, silicon dioxide and zirconium oxide) constitutes 10% of the total dry mixture, and that the proportion of silicon dioxide in the additive is 15%. Thus, silicon dioxide represents 15% of the 10% of the total dry mixture, or 1.5%. No aluminum oxide or zirconium oxide is added to the mixture. Regarding the results of Experiment 13, the initial setting time is reduced compared to the control sample and compared to Experiments 10 to 12. The final setting time is reduced compared to the control sample and Experiments 10 and 12, but increased compared to Experiment 11. The compressive strength at 4 hours is increased compared to Experiments 10 and 11; at 5 o'clock, it is increased compared to Experiments and 11; at 7 hours, it is increased compared to the control sample and to Experiment 12, but reduced compared to Experiments 10 and 11; at 8 a.m., it is increased compared to the control sample and

  to Experiment 12, but reduced compared to Experiments

  meetings 10 and 11; at 1 day, it is increased compared to the control sample and to Experiment 12, but reduced compared to Experiments 10 and 11; and at 7 days, it is increased compared to the control sample and to Experiment 12, but reduced compared to Experiments and 11. The exothermic peak is increased compared to the control sample and to Experiment 12 and decreased compared to Experiments 10 and 11. The average speed of temperature rise is increased compared to

  the control sample and Experiments 10 to 12.

  Experiment 14 In Experiment 14, the percentage of cement rich in Alumina Secar 51 remains the same as for the control sample, that is to say 50%; however, the sand content is lowered to 49.9% and zirconium oxide is added in an amount of 0.1% of the total mixture. The proportion of zirconium oxide, 0.1% of the total mixture, is chosen assuming that the total additive (containing aluminum oxide, silicon dioxide and zirconium oxide) constitutes% of the dry mixture total and that the proportion of zirconium oxide in the additive is 2%. Thus, zirconium oxide represents 2% of the 5% of the total dry mixture, or 0.1%. No aluminum oxide or silicon dioxide is added to the mixture. Regarding the results of Experiment 14, the initial setting time is the same as for the control sample and the final setting time is almost the same as for the control sample. The initial compressive strengths (up to 1 day) are increased compared to the control sample and Experiment 12, but are reduced compared to Experiments 10, 11 and 13. The compressive strength at 7 days is increased compared to the control sample and to Experiment 12, but is reduced compared to Experiments 10, 11 and 13. The exothermic peak temperature is increased compared to the control sample and to Experiment 12, but decreased compared to Experiments 10, 11 and 13. The average temperature rise speed is increased compared to the control sample, remains the same compared to Experiment 12,

  and is decreased compared to Experiments 10, 11 and 13.

  Experiment 15 In Experiment 15, the percentage of cement rich in Alumina Secar 51 remains the same as for the control sample, that is to say 50%; however, the sand content is lowered to 48.5% and zirconium oxide is added in an amount of 1.5% of the total mixture. The proportion of zirconium oxide, 1.5% of the total mixture, is chosen assuming that the total additive (containing aluminum oxide, silicon dioxide and zirconium oxide) constitutes 10% of the mixture total dry and the proportion of zirconium oxide in the additive is 1.5%. Thus, zirconium oxide represents 15% of the 10% of the total dry mixture, or 1.5%. No aluminum oxide or silicon dioxide is added to the mixture. With regard to the results of Experiment 15, the initial setting time is less than those of the control sample and of Experiment 14, but greater than those of Experiments 10 to 13. The final setting time is less than those in the control sample and in Experiment 14, but higher than those in Experiments 10 to 13. The compressive strength at 7 and 8 hours is increased compared to the control sample and in Example 14, but reduced compared to Experiments at 13. The compressive strength at 1 day is increased compared to the control sample and at Experiments 12 and 14, but reduced compared to Experiments 10, 11 and 13. The compressive strength at 7 days is increased compared to the control sample and to Experiment 12, is the same as for Example 14 and reduced comparatively

  Experiments 10, 11 and 13. The peak temperature exo-

  is increased compared to the sample

  witness and to Experiments 12 and 14, and decreased comparison

  vement in Experiments 10, 11 and 13. The average speed of temperature rise is increased compared to the control sample and in Experiments 12 and 14, and

  decreased compared to Experiments 10, 11 and 13.

  The following Table 4 gives the results of Experiments 10 to 15. When the proportion of additive is

  lower than that of Experiments 10 to 15, the accelerated effect

  erator is insignificant or null. In the higher proportions of additive, other unacceptable properties are manifested

  (for example the material is too rigid to be properly compacted).

TABLE 4

  Experience No WITNESS 10 i 1 12 132 13 14 15

INGREDIENTS,%

  CRA (Secar 51) 50.0 50.0 50 o, o 50.050.0 50.0 50.0

A1203 - 3.5 9.6 - - - -

SiO2 - - - 0.1 1.5 - -

  ZrO2 - - - - - 0.1 1.5 Sand 50.0 46.5 40.4 49.9 48.5 49.9 48.5 Mixing water, 20 2 FOR ALL MIXTURES% by weight of the dry mixture

PROPERTIES

  Setting time, min Initial 312 169 144 277 141 312 285 Final 357 192 169 320 173 356 332 Compressive strength, MPa (psi)

3 h - _ 2.41 - - - -

(350)

4 h - 5.69 13.44 - 24.13 - -

(825) (1950) (3500)

h - 39.47 38.96 - 44.13 - -

(5725) (5650) (6400)

6 h - 51.88 52.23 - 45.51 - -

(7,525) (7,575) (6,600)

  7 h 0.86 55.50 54.47 9.31 48.95 1.21 5.52

  (125) (8050) (7900) (1350) (7100) (175) (800)

  8 h 7.58 56.02 55.85 34.54 49.30 8.27 33.44

  (1100) (8125) (8100) (5010) (7150) (1200) (4850)

  1 day 43.61 58.43 56.88 46.88 55.16 47.23 48.61

  (6325) (8475) (8250) (6800) (8000) (6850) (7050)

* 7 days 57.57 73.43 72.74 58.26 67.57 58.95 58.95

  (8350) (10650) (10550) (8450) (9800) (8550) (8550)

  Exothermic peak Temperature, C (F) 103.3 116.1 117.2 100.6 111.1 105.6 107.8

  (218) (241) (243) (213) (232) (222) (226)

  Time, min 513 339 371 463 293 486 450 Average temperature rise speed, 0.161 0.278 0.261 0.172 0.305 0.172 0.194 C / min (F / min) (0.29) (0.50) (0.47 ) (0.31) (0.55) (0.31) (0.35) Experiments 16 and 17 General Experiments 16 and 17 were designed to determine the effect of certain plasticizers on the cement-based composition . The plasticizers are Lomar DF, which contains an anti-foaming agent and which is sold by Henkel Corp., and MCG SC9, which is sold by Morristown Chemical Group. Plasticizers may include naphthalene sulfonate compounds, melamine sulfonate compounds, and lignosulfonate compounds. Experiment 16 The control sample comprises a mixture of cement rich in Secar 51 alumina with sand. The dry mixture

  of the control sample contains 50% of cement rich in Secar 51 alumina, 49.9% of sand and 0.1% of MCG-SC9.

  The water content of the composition is 16.5% of the weight of the dry matter. In Experiment 16, the percentage of cement rich in Secar 51 alumina remains the same as for the control sample, that is to say 50%; however, the sand content is lowered to 44.9%, and MCG-SC9 is added in a proportion of 0.1% of the total mixture. The proportion of water is raised to 18.75% of the weight of the dry matter. An additive consisting of 4.15% aluminum oxide, 0.425% silicon dioxide and 0.425% zirconium oxide is included in the mixture. As for the results of Experiment 16, the final setting time is reduced compared to the control sample (because of the previously observed retarding effect of the plasticizer, the initial setting time did not measured, as well as the compressive strength at 6 or 8 hours). The compressive strengths at 1 day and 7 days are increased compared to the control sample, and the exothermic peak and the average temperature rise speed are

  both increased compared to the control sample.

  Experiment 17 The control sample contains a mixture of Portland cement, type II, sold by Lehigh Portland Cement Company, with sand. The dry mixture of the control sample contains 50% of this cement, 49.8% of sand and 0.2% of Lomar DF. The water content of the composition is 18.25% of the weight of the dry matter. In Experiment 17, the percentage of Lehigh type II cement remains the same as for the control sample, ie 50%; however, the sand content is lowered to 44.8%, and Lomar DF is added in an amount of 0.2% of the total mixture. An additive consisting of 4.15% aluminum oxide, 0.425% silicon dioxide and

  0.425% zirconium oxide is included in the mixture.

  Regarding the results of Experiment 17, the initial and final setting times are reduced compared to the control sample. The compressive strengths at 8 hours, 1 day and 7 days are increased compared to the control sample, and the exothermic peak and the average rate of temperature rise are both increased compared to the control sample. The results of

  Experiments 16 and 17 are presented in Table 5.

TABLE 5

  Experience N WITNESS 16 | TMIN 17

INGREDIENTS,%

  CRA (Secar 51) 50.0 50.0 Portland (Lehigh T-II) - - 50.0 50.0 ASZ additive, total - 5.0 - 5.0 including: A1203 - 4.15 - 4.15 SiO2 - 0.425 - 0.425 ZrO2 - 0.425 - 0.425 1 0 Agents reducing the water content Lomar DF - - 0.2 0.2

MCG-SC9 0.1 0.1 - -

  Sand 49.9 44.9 49.8 44.8 Mixing water 16.5 18.75 18.25 18.75 i 5 PROPERTIES Setting time, min Initial - - 247 204 Final 887 819 367 340 Resistance to compression , MPa (psi)

6 a.m. .

8 h - - 1.72 4.14

(250) (600)

1 day 20.68 74.46 31.03 33.96

(3000) (10800) (4500) (4925)

7 days 47.75 87.56 48.95 53.26

(6,925) (12,700) (7,100) (7,725)

  Exothermic peak Temperature, C (F) 53.3 67.2 48.9 55.0

(128) (153) (120) (131)

  Time, min 3,175 1,495 520,417 Average speed of temperature rise, C / min (F / min) 0.011 0.033 0.050 0.078

(0.02) (0.06) (0.09) (0.14)

  Experiments 18 and 19 General Experiments 18 and 19 were designed to determine the effect, on the cement-based composition, of the presence of certain agents releasing air and / or gas generators. The air releasing agent is fluidized coke sold by Five Star Products, Inc. under the trademark "PLA" (hereinafter "PLA") and the gas generating agent is azodicarbonamide sold by Uniroyal Chemical under the trademark "AZ-130" (hereinafter "AZ-130"). The water content for Experiments 18 and 19, as well as their respective control samples, is 20% by weight

dry mix.

  Experiment 18 The control sample comprises a mixture of cement rich in Secar 51 alumina with sand. The dry mixture of the control sample comprises 50% of cement rich in

  Secar 51 alumina, 47% sand and 3% PLA.

  In Experiment 18, the percentage of cement rich in alumina Secar 51 remains the same as for the control sample, that is to say 50%; however, the sand content is lowered to 42%, and PLA is included in a proportion of 3% of the total mixture. An additive consisting of 4.15% aluminum oxide, 0.425% silicon dioxide and

  0.425% zirconium oxide is included in the mixture.

  Regarding the results of Experiment 18, the initial and final setting times are reduced compared to the control sample. In the plastic state, the change in volume of the composition is less than the change in volume of the control sample. Compressive strengths at 7 hours, 8 hours and 1 day are increased

  compared to the control sample, and the exother-

  mic and the average speed of temperature rise are

  both increased compared to the control sample.

  Experiment 19 The control sample comprises a mixture of cement rich in Alumina Secar 51 with sand. The dry mixture of the control sample comprises 50% of cement rich in

  Secar 51 alumina, 49.99% sand and 0.01% AZ-130.

  In Experiment 19, the percentage of cement rich in alumina Secar 51 remains the same as for the control sample, that is to say 50%; however, the sand content

  is lowered to 44.99% and AZ-130 is included in a proportion

  0.01% of the total mixture. An additive consisting of 4.15% aluminum oxide, 0.425% silicon dioxide and 0.425% zirconium oxide is included in the mixture. Regarding the results of Experiment 19, the initial and final setting times are reduced compared to the control sample. In the plastic state, the change in volume of the composition is less than the change in volume of the control sample. Resistance to

  compression at 1 day are increased compared to the sample

  control tillon, and the exothermic peak and the average speed

  temperature rise are both increased compara-

  the control sample. The following Table 6 gives

  the results of Experiments 18 and 19.

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  6L NIO3.i | L NIOW31I oN oDUBT.sddX 9 nV3S19Vi Experiment 20 Experiment 20 is designed to determine the effect,

  on the cement-based composition of a entraining agent

  air, a vinol resin (hereinafter "NVX").

  The control sample comprises a mixture of Secar 51 alumina-rich cement with sand. The dry mixture of the control sample comprises 50% of cement rich in Secar alumina, 49.99% of sand and 0.01% of NVX. The water content of Experiment 20 is 20% of the weight of the dry mixture. In Experiment 20, the percentage of cement rich in alumina Secar 51 remains the same as for the control sample, that is to say 50%; however, the sand content is lowered to 44.99% and NVX is included in a proportion of 0.01% of the total mixture. An additive consisting of 4.15% aluminum oxide, 0.425% silicon dioxide and

  0.425% zirconium oxide is included in the mixture.

  Regarding the results of Experiment 20, the initial and final setting times are reduced compared to the control sample. The compressive strengths at 7 hours, 8 hours and 1 day are increased compared to the control sample, the exothermic peak remains the same as for the control sample and the average speed of temperature rise is increased compared to the sample

  witness. The results of Experiment 20 are presented in Table 7.

TABLE 7

Experiment No WITNESS 20

INGREDIENTS,%

  CRA (Secar 51) 50.0 50.0 Additive ASZ, total - 5.0 including: A1203 - 4.15 SiO2 - 0.425 ZrO2 - 0.425

NVX 0.01 0.01

  Sand 49.99 44.99 Mixing water,% 20.0

PROPERTIES

  Setting time, min Initial 290 211 Final 345 241 Compressive strength, MPa (psi) 4 h h - 13.62

(1975)

6 h 2.07 25.17

(300) (3650)

7:19 a.m. 34.65

(2900) (5025)

8 h 29.99 36.37

(4350) (5275)

1 day 41.20 46.88

(5975) (6800)

  Exothermic peak Temperature, C (OF) 105.6 105.6

(222) (222)

  Time, min 636,443 Average temperature rise speed, C / min (F / min) 0.133 0.183

(0.24) (0.33)

  Experiment 21 Experiment 21 is designed to determine the effect of a corrosion inhibitor, NaNO2, on the composition to

cement base.

  The control sample comprises a mixture of Portland cement, type II, with sand. The dry mix of the sample

  control sample comprises 50% of this cement, 49.0% of sand and 1% of NaNO2. The water content of Experiment 21 is 5-20% of the weight of the dry mixture.

  In Experiment 21, the percentage of Portland cement, type II, remains the same as for the control sample, that is to say 50%; however, the sand content is lowered to 44% and NaNO2 is included in a proportion of 1% of the total mixture. An additive consisting of 4.15% aluminum oxide, 0.425% silicon dioxide and 0.425% zirconium oxide is included in the mixture. With regard to the results of Experiment 21, the initial and final setting times are reduced compared to the control sample15. The compressive strengths

  6 hours, 7 hours, 8 hours and 1 day are increased compared to

  relative to the control sample, and the exothermic peak and the average rate of temperature rise are both increased compared to the control sample. The

  results of Experiment 21 are presented in Table 8.

TABLE 8

Experiment No WITNESS 21

INGREDIENTS,%

  Portland, T-II 50.0 50.0 Additive ASZ, total - 5.0 including: A1203 - 4.15 SiO2 - 0.425 ZrO2 - 0.425 NaNO2 1.0 1.0 Sand 49.0 44.0 Mixing water, % 20.0

PROPERTIES

  Setting time, min Initial 228 224 Final 324 303 Compressive strength, MPa (psi) 6 h 0.86 0.86

(125) (125)

7 h 1.72 1.90

(250) (275)

8 h 2.76 3.45

(400) (500)

1 day 23.10 27.58

(3350) (4000)

  Exothermic peak Temperature, C (F) 47.8 50.0

(118) (122)

  Time, min 533 503 Average temperature rise speed, C / min (F / min) 0.044 0. 055

(0.08) (0.1)

  Experiment 22 Experiment 22 is designed to determine the effect on the cement-based composition of the presence of a mineral additive, a class C fly ash. The control sample comprises a mixture of cement

  Portland, type II, with sand. The dry mix of the sample

  control sample contains 40% cement, 50% sand and% Class C fly ash. The water content of the control sample and Experiment 22 is 20% of the

weight of dry matter.

  In Experiment 22, the percentage of Portland cement, type II, remains the same as for the control sample, ie 40%; however, the sand content is lowered to 40% and the fly ash, Class C,

  is added in a proportion of 10% of the total mixture.

  An additive consisting of 8.3% aluminum oxide, 0.85% silicon dioxide and 0.85% zirconium oxide is included in the mixture. Regarding the results of Experiment 22, the initial and final setting times are reduced compared to the control sample. The compressive strengths at 8 hours, 12 hours and 1 day are increased compared to the control sample, and the exothermic peak and the average temperature rise speed are both increased compared to

the control sample.

  The results of Experiment 22 are presented to

Table 9.

TABLE 9

Experiment N WITNESS 22

INGREDIENTS,%

  Portland T-II 40.0 40.0 Class C fly ash 10.0 10.0 ASZ additive, total - 10.0 including: A1203 - 8, 3 SiO2 - 0.85 ZrO2 - 0.85 1 0 Sand 50 , 0 40.0 Mixing water,% 20.0

PROPERTIES

  Setting time, min Initial 334 235 Final 432 325 Compressive strength, MPa (psi) 6 h 8 h 0.34 1.21

(50) (175)

12.35 6.89

(500) (1000)

1 day 16.03 19.65

(2325) (2850)

  Exothermic peak Temperature, C (F) 42.2 42.8

(108) (109)

  Time, min 720,588 Average temperature rise speed, C / min (F / min) 0.028 0.033

(0.05) (0.06)

  It goes without saying that the invention is not limited to the embodiments described here and that those skilled in the art can produce various variants thereof without departing from its scope.

Claims (17)

  1. Cement composition, comprising an additive consisting of aluminum oxide, silicon dioxide and zirconium oxide, so that the composition, when mixed with water, is capable to set in a hard mass with abbreviated initial and final setting times and with a higher average speed of heat release comparatively   to the same composition not containing the additive.   2. Cement-based composition as claimed   cation 1, characterized in that the aluminum oxide is present in a proportion of 70 to 96% by weight of   the additive, sodium dioxide is present in a proportion   tion of 2 to 15% by weight of the additive and zirconium oxide is present in a proportion of 2 to 15% by weight of the additive.   3. Cement-based composition as claimed   cation 1 or 2, characterized in that it further comprises a cement rich in alumina.   4. Cement-based composition as claimed   cation 1 or 2, characterized in that it further comprises Portland cement.   5. Cement-based composition as claimed   cation 1 or 2, characterized in that it further comprises   an alumina-rich cement and a Portland cement.   6. Cement-based composition as claimed   cation 1, 2, 3, 4 or 5, characterized in that it additionally comprises a plasticizing agent, reducing the water content and defoamer.   7. Cement-based composition as claimed   cation 6, characterized in that the plasticizing agent, reducing the water and defoaming content is a compound   based on naphthalene sulfonate, melamine sulfonate or ligno- sulfonate.   8. Cement-based composition as claimed   cation 1, 2, 3, 4 or 5, characterized in that it comprises   moreover an agent releasing air and / or gas generator.   9. Cement composition according to claim 8, characterized in that the air releasing agent and / or gas generator is fluidized coke and the generating agent gas is azodicarbonamide.   10. Cement-based composition according to claim 1, 2, 3, 4 or 5, characterized in that it comprises   plus an air entraining agent.   11. Cement-based composition as claimed   cation 10, characterized in that the entraining agent of air is a vinsol resin.   12. Cement-based composition as claimed   cation 1, 2, 3, 4 or 5, characterized in that it contains additionally a corrosion inhibitor.   13. Cement-based composition as claimed   cation 12, characterized in that the corrosion inhibitor is sodium nitrite.   14. Cement-based composition as claimed   cation 1, 2, 3, 4 or 5, characterized in that it comprises additionally a mineral additive.   15. Cement-based composition as claimed   cation 14, characterized in that the mineral additive is fly ash.   16. Method for shortening the setting time, increasing the initial compressive strength and increasing the average rate of heat generation of a cement-based system, characterized in that it consists in adding to the system an additive comprising aluminum oxide,   silicon dioxide and zirconium oxide.   17. The method of claim 16, characterized in that the added aluminum oxide is present in a proportion of 70 to 96% by weight of the additive, the added silicon dioxide is present in a proportion of 2 to 15 % by weight of the additive and the zirconium oxide added is   present in a proportion of 2 to 15% by weight of the additive.