Process for the preparation of cement, mortars, concrete compositions containing a calcium carbonate—based filler (pre)—treated with a superplasticizer, compositions and cement products obtained and their applications

Abstract

The invention concerns a PROCESS for the preparation of cement/mortar/concrete (for simplicity: cement) compositions or systems, (hereafter cement compositions or systems for simplicity), of a general known type, in which the filler(s) is/are comprising or consist of calcium carbonate-based filler(s), comprising at least one step where the said filler(s) is/are treated with an efficient treating amount of at least one treating agent consisting of or comprising superplastifier(s). The main purpose of this invention is to build a process aimed at providing improved, High performance, FLUID, cement or mortars or concrete systems or compositions having an improved compacity, an improved flowability, and globally speaking a definitely improved workability, and regularity of the properties of the final systems. The present invention also concerns a filler for cement compositions, characterized in that if consists of, or comprises, a calcium-carbonate-based filler or blends of same, pre-treated with an efficient amount of at least one superplastifier.

Claims

1. A cement composition comprising (i) cement, (ii) calcium carbonate surface treated with 0.02 to 0.15 wt. %, based on the dry weight of the cement composition, of a treatment agent comprising at least one superplasticizer and at least one plasticizer, wherein the ratio of the superplasticizer and the plasticizer is from 95/5 to 85/15 on a dry weight basis, and wherein the calcium carbonate is surface treated with the treatment agent before being introduced into the cement composition, and (iii) optionally one or more of an aggregate, sand, gravel, a hydraulic binder, an air entrainment agent, a setting retarder, a setting accelerator, an anti-foam agent, an adjuvant, a fluidifier and water.

2. The cement composition according to claim 1, wherein the calcium carbonate is calcium carbonate, ground calcium carbonate, precipitated calcium carbonate or a blend of ground calcium carbonate and precipitated calcium carbonate.

3. The cement composition according to claim 1, wherein the superplasticizer is selected from the group consisting of a polycarboxylate, a polycarboxylate ether, a sulfonated naphthalene condensate, and a sulfonated melamine formaldehyde.

4. The cement composition according to claim 1, wherein the superplasticizer is a polycarboxylate or a polycarboxylate ether.

5. The cement composition according to claim 1, wherein at least 80% of the surface of particles of calcium carbonate is covered with the at least one superplasticizer.

6. The process according to claim 1, wherein at least 90% of the surface of particles of calcium carbonate is covered with the at least one superplasticizer.

7. The cement composition according to claim 1, wherein 100% of the surface of particles of calcium carbonate is covered with the at least one superplasticizer and the plasticizer.

8. The cement composition according to claim 1, containing 0.3 to 3 kg of the at least one superplasticizer per 100 kg of the cement composition.

9. The cement composition according to claim 1, containing 0.8 to 1.2 kg of the at least one superplasticizer per 100 kg of the cement composition.

10. The cement composition according to claim 1, further comprising an aggregate, a hydraulic binder, an air entrainment agent, a setting retarder, a setting accelerator, an anti-foam agent, an adjuvant, and a fluidifier.

11. The cement composition according to claim 1, further comprising an aggregate, a hydraulic binder, an air entrainment agent, a setting retarder, a setting accelerator, an anti-foam agent, an adjuvant, a fluidifier, and water.

12. The cement composition according to claim 1, further comprising an aggregate, sand, a hydraulic binder, an air entrainment agent, a setting retarder, a setting accelerator, an anti-foam agent, an adjuvant, and a fluidifier.

13. The cement composition according to claim 1, further comprising an aggregate, sand, a hydraulic binder, an air entrainment agent, a setting retarder, a setting accelerator, an anti-foam agent, an adjuvant, a fluidifier and water.

14. The cement composition according to claim 1, further comprising an aggregate, sand, gravel, a hydraulic binder, an air entrainment agent, a setting retarder, a setting accelerator, an anti-foam agent, an adjuvant, and a fluidifier.

15. The cement composition according to claim 1, further comprising an aggregate, sand, gravel, a hydraulic binder, an air entrainment agent, a setting retarder, a setting accelerator, an anti-foam agent, an adjuvant, a fluidifier and water.

16. The cement composition according to claim 2, further comprising an aggregate, a hydraulic binder, an air entrainment agent, a setting retarder, a setting accelerator, an anti-foam agent, an adjuvant, and a fluidifier.

17. The cement composition according to claim 2, further comprising an aggregate, a hydraulic binder, an air entrainment agent, a setting retarder, a setting accelerator, an anti-foam agent, an adjuvant, a fluidifier, and water.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1: correspond to a surface treatment with the superplastifier A described above at a dosage of such as expressed in the corresponding Table 1.

(2) FIG. 2: correspond to a surface treatment with the superplastifier B described above at a dosage of such as expressed in the corresponding Table 2.

(3) FIG. 3: correspond to a surface treatment by the product NRG 100 at a dosage such as expressed in the corresponding Table 3.

(4) FIG. 4: correspond to a surface treatment with the superplastifier A described above at a dosage of such as expressed in the corresponding Table 4.

(5) FIG. 5: correspond to a surface treatment with the superplastifier B described above at a dosage of such as expressed in the corresponding Table 5.

(6) FIG. 6: correspond to a surface treatment by the product NRG 100 at a dosage such as expressed in the corresponding Table 6.

DETAILED DESCRIPTION OF THE INVENTION

(7) In a detailed and most preferred (best mode as of today) embodiment, the said PROCESS for preparing the said cement compositions or systems is characterized (in the so-called pre-treatment or (in the Tables 1-6 namely) equivalently initial mode) by a) providing a powder of dry calcium carbonate(s) filler as defined above as calcium carbonate(s)-based filler, hereafter filler or filler(s); b) mixing the said filler(s) with an efficient treating amount of at least one superplastifier, thus producing pre-treated filler(s), c) introducing the said pre-treated filler(s) into a kneading or mixing device already containing mix water or a composition of mix water possibly containing routine or non-interfering additives (mix water composition) (hereafter for simplicity mixing water) d) optionally adding before or after the step c), preferably before, aggregates such as sand and/or gravel, and possibly other non interfering routine additives or adjuvants, e) kneading or mixing the said load during an efficient period of time, f) recovering the said cement composition.

(8) By not interfering, it is meant not interfering or not noticeably with the said considered treatment or inventive process.

(9) By efficient period of time, it is meant a total period of time leading to an homogeneous mixture or blend, in the order of 2-15 min, preferably, for the standard mixtures or blends, 30-60 s. This will be detailed hereafter.

(10) An example of end-user application is as follows: if the end user targets medium or standard properties for its final cement composition, for example with a final mixing within his facilities in a fixed installation etc., he will use compositions which are correspondingly simple that is not specifically complex or sensitive in terms of routine additives, superplastifier, filler etc; therefore, the end user will have to mix for a relatively short time such as the above 35-65 s.

(11) If to the contrary the end user targets high-level or very HP properties, he will use correspondingly more complex compositions and more sensitive components, for example a more sensitive filler or superplastifier, or sensitive routine additives aimed at reaching a specific property, etc. . . . and usually he will use less or far less mixing water: therefore he will need to mix for a much longer time such as the above 1-3 to 10-15 min.

(12) Evidently, technical composition or system means a HP quality (see the Self levelling test section above) or FLUID see above too, and by contrast a standard final composition means a non-HP quality, that is, see above, dry or more likely plastic.

(13) In both cases, that is technical or standard compositions, and as explained in the present application, the common objective is to reach a homogeneous composition, also as explained specifically in the present application, see below The main essential crieteria . . . final product must be homogeneous.

(14) The above working principals are well known to the skilled man and are for completeness only. The above values and examples are to provide guidelines only, which the skilled man will be able to easily use in order to meet the essential main criteria.

(15) One will understand that it is impossible to provide examples or data for any type of ultimate composition or ingredient, since the interactions are complex, so are the kinetics etc. . . . but the skilled man knows about those parameters.

(16) According to a less preferred mode, the said PROCESS for preparing the said cement compositions or systems is characterized in the mixed-treatment mode by a) providing a powder of dry calcium carbonate (s) filler as defined above b) mixing the said filler(s) with a portion or part of an efficient treating amount of at least one superplastifier, thus producing the partially pre-treated filler (s), c) introducing the said partially pre-treated filler(s) into a kneading or mixing device already containing mix water or a composition of mix water possibly containing routine additives (mix water composition) (hereafter for simplicity mixing water) d) introducing before or during step c), preferably during, into the said kneading or mixing device, the rest of the said efficient treating amount or proportion of the superplastifier(s) e) optionally adding before or after the steps c) and d), preferably before, aggregates such as sand and/or gravel, and possibly other routine additives not interfering with the said treatment, f) kneading or mixing the said load during an efficient period of time g) recovering the said cement composition.

(17) According to still another embodiment, the said PROCESS for preparing the said cement compositions or systems is characterized in the inside-treatment mode by a) providing a powder of dry calcium carbonate (s) based filler(s) as defined above b) introducing the said un-treated filler(s) into a kneading or mixing device already containing an efficient treating amount of at least one superplastifier, (or receiving it just after the introducing of the said un-treated filler(s)) mix water or a composition of mix water possibly containing routine additives (mix water composition) (hereafter for simplicity mixing water) c) kneading or mixing the said load during an efficient period of time d) optionally adding before or after the step c), preferably before, aggregates such as sand and/or gravel, and possibly other routine additives or adjuvants, not interfering with the said treatment, e) recovering the said cement composition.

(18) By just after it is meant that the treating agent can be introduced before of after the un-treated filler(s), bur in the second case it must be introduced rapidly after the filler(s), say, in a matter of some seconds to 10 s or so, in order for the filler to remain fully available for the treating agents without any disturbance due to the kneading or mixing with sand, gravel etc.

(19) It is usually most preferred to first introduce the aggregates such as sand and gravel into the kneading or mixing device, and mix them optionally with a small amount of water and/or of fluidifier (see above), before performing the other steps.

(20) As treatment agent, is used at least one superplastifier (and possibly at least one superplasticizer with possibly some inert amount of plasticizer).

(21) According to the above definition of the treating agent, the so called treating agents for the fillers consist of/or comprise superplastifier(s), or comprise at least one superplastifier (and optionally at least one plastifier in order to reduce the overall costs), and preferably consist of at least one superplastifier and optionally at least one efficiently cost-reducing amount of plastifier, and most preferably one superplastifier and optionally one efficiently cost-reducing amount of a plasticizer.

(22) Superplastifiers are well-known agents and are to the best selected among the following products or families and their blends:

(23) Polycarboxylates, polycarboxylate ethers, or much less preferred products manufactured from sulfonated naphthalene condensate or sulfonated melamine formaldehyde. The skilled man knows these products, which are additionally disclosed in the prior art as cited above.

(24) In this invention, the best mode treating agents (product A and product B) appear to be, in the superplastifiers families, of the polycarboxylate ether formulae.

(25) To be noted, the products codes A to K in Table A are FILLERS to be characterized, NOT to create a confusion with the preferred treating agent(s) A and B above which are (superplastifiers(s)).

(26) By efficient period of time it is meant here a period of time of about 35-65 s for the standard compositions, and from 1-3 to 10-15 min. for the more technical that is more complex and/or more sensitive compositions, as is known from the skilled man. For a standard composition, an example can be a kneading time of 10-15-20 s for the gravel and sand (dry kneading or mixing is preferred), then of 10 s for the kneading or mixing of the hydraulic binder and untreated filler, then 10-15 s for the kneading or mixing with the treatment agent(s) and mix water (this in the so-called inside treatment mode), then 5-15 s for the final kneading or mixing with the final routine additives.

(27) The main and essential criteria for the said period of mixing is that the final product must be homogeneous and the treating agent(s) be not absorbed or adsorbed onto the sand or gravel, or the less possible extent.

(28) By efficient amount of plasticizer (when present with the superplastifier) it is meant in this application an amount or proportion of plastifier which is able to reduce the cost of the treatment without interfering negatively with the system and namely the filler(s) behaviour, namely in terms of surface activity and reactivity); the same criteria applies to the inert additives.

(29) By comprising we mean here that the said treatment agents consist essentially or entirely of superplastifier(s) as defined, and may contain as explained a cost-reducing efficient amount of at least one plastifier, and may also contain inert additives useful for the intended final application, such as anti foam agents, retarders, accelerators etc. absolutely known to the skilled man.

(30) Usual additives of inert nature can be added at injection points known to the skilled man, as said earlier.

(31) The mixing or kneading device can be operated in a batch mode, a semi-continuous mode, or a continuous mode, the adaptations being within the easy reach of an average skilled man.

(32) Actually, it has been surprisingly discovered that such superplastifier(s) previously used as mere fluidifiers are able to UPGRADE FILLERS from medium, and sometimes from low, to HP grade.

(33) Dosage of Superplastifier(s) Used for the Pre-Treatment and Treatment of the Filler(s)

(34) At the end-user location, the dosage in superplastifier(s) is ranging from 0.3 to 3 kg for 100 kg of cement, preferably 0.8 to 1.2 kg/100 kg of cement, on a DRY/DRY basis.

(35) In laboratory conditions, the same proportion ranges from 0.05 to 0.1% by weight of the carbonate (DRY) that is 0.1 to 0.3 kg/100 kg of cement, on a DRY/DRY basis.

(36) In laboratory conditions, for establishing the Table A, one used from 0.8 to 1.1 kg/100 kg cement, on a DRY/DRY basis.

(37) At the end user location, the ratio superplastifier(s)/plasticizer(s) can be from 100/0 to 95/5-90/10, preferably no less than 85/15 on a weight dry basis.

(38) The invention also resides in the said CEMENT (in the broad sense given above that is cement, cementitious compositions, mortars, concretes) COMPOSITIONS (OR SYSTEMS): per se, since they are distinguishable from the prior art similar compositions by their physical structure and their properties, or as prepared by the above process of the invention,
and in the USE of those cement systems or compositions for making concrete elements,
and ultimately in the CEMENT ELEMENTS per se, since they are distinguishable for the same reasons as the compositions, and as prepared by using the said compositions. as well as in the calcium carbonate-based filler(s) as pre-treated by the pretreatment process of the invention.

(39) Another objective is evidently to meet Client's requirements which are that the galette or cone be above 250 mm in diameter, most preferably 300 mm, or still better, above 300 mm, at a cost-effective dosage.

(40) Some filler-containing compositions meet that requirement, depending on the origin of the filler. This can be easily and quickly appreciated by a skilled man by performing the cone and plate test.

(41) This test allows therefore to discriminate the fillers and select the best-performing filler and even the best performing superplastifier(s), in view of the final properties required by the end user.

(42) Many do not meet that requirement, certain by far.

(43) Usually (PRIOR ART PROCESS) the test is conducted on an UNtreated filler

(44) In the present application the superplastifiers are used as treatment agents for the filler in a specific and inventive process.

(45) Another objective of the invention is therefore to upgrade medium or low quality, filler-containing, cement/mortar/concrete (for simplicity, cement) compositions or systems to HP (or high performance) compositions, by introduction in the mixing/kneading device of the said superplastifier(s) and optionally (see above) at least one cost-reducing efficient amount of plastifier(s) in order to improve the behaviour of the filler(s) and therefore of the overall composition.

(46) Plastifiers(s) are selected preferably among those cited above.

(47) Those families are very well known to the skilled man. The merit of the inventors was not to discover those families, nor their use as superplastifiers in the common sense of the prior art, but to discover that one can WIDELY UPGRADE A CEMENT FILLER (and hence the cement compositions) BY TREATING the Calcium Carbonate-based fillers with such species.

(48) It has been noted that certain compositions are so low in cone diameter (self levelling test), stickiness, etc. that there is no way to upgrade them; this demonstrates the difficulty of the invention's task.

(49) Some can be upgraded but only by adding large proportions of the superplastifers used according to the invention and even in such cases, the diameter requirement can be matched, BUT the galette or cone remains sticky and thick in consistency, what means that the result, despite the fact that the diameter of the galette is correct, the composition cannot be regarded as upgraded to HP concrete composition.

(50) It is necessary to keep in mind that, for a concrete composition or system to be acceptable as HP composition, or upgraded from low or medium quality to HP quality, TWO features MUST be met simultaneously: the diameter of the galette or cone must be above about 250, or better above 300, or still better above 350 mm, AND the galette or cone must NOT be sticky or thick in consistency.

(51) This is another measurement of the very tough challenge which this invention wishes to overcome, and of the very high technical and scientific input brought by the invention to the current state of the art.

(52) As can be seen from the attached Table A, the poor fillers can NOT be upgraded since they never meet BOTH features.

(53) This is also true for some medium fillers such as product D, B, G, I and K which may show a good fluidity for example at a dosage of 4 g BUT have a bad aspect or handling behaviour.

(54) With the help of the Table A and of the above and below comments, the skilled man will be able to discriminate the fillers which CAN be upgraded by the invention, and those (regarded as low as per the test of the Table A) which can NOT.

(55) To achieve these objectives, the skilled man bears in mind first that a certain water/cement ratio is directly linked to the workability of the composition and that it is also imperative to develop high performance qualities in the end product, such as high performance or technical level of setting properties, drying properties, mechanical strength, namely compressive strength etc.

(56) As specified above, the invention relies first on the surface treatment of the CaCO.sub.3-based FILLER(s) by one or more superplasticizer(s) (optionally in admixture with one or more plastifier). The amount of plastifier will be calculated easily by the skilled man as being the efficient cost effective amount, not interfering with the overall treatment, see above.

(57) Two superplastifiers products are providing the best results. They are the best mode as of the filing date (products A and B of the polycarboxylate ether family) as mentioned above.

(58) It is very surprising to notice that when using the invention, proportions of superplastifier(s) treating agent(s) for the CaCO.sub.3 filler(s) as low as 0.03 or 0.05 to 0.1% are sufficient. It is entirely surprising to notice that such minuscule amounts of treating agents are capable of upgrading to HP quality even medium to poor fillers.

(59) Many such plasticizers, superplasticizers or fluidifiers, are known, such as described for example in the CHRYSO patent EP 0 663 892

(60) Other products have been successfully tested as superplastifiers) usable in the process of the invention to perform a surface treatment of the carbonate filler, such as the CHRYSO products described in the above cited EP patent, such as PREMIA 196, or NRG 100 from Mappei.

(61) Some usual additives may be routinely added such as air entrainment agents, setting retarders or accelerators etc. at a place which is known from the skilled man, for example with the water or after the superplastifiers are added.

(62) As to the powders that is the cement and the filler, the cement can be added first, then the filler, or the reverse, or they can be introduced together as a premix.

(63) It is however preferred to introduce the cement and the filler together as a premix, so as to better ensure that both powders will be homogeneously mixed with and wet with the water.

(64) The above are batch modes.

(65) One can also think of continuous modes such as performing the addition in one of the above orders, for example in a kneading or mixing device equipped with an endless screw (with additions at various points along the length of the equipment), possibly with pre-mixes being added at some point(s), or as another example in a series of successive kneading or mixing devices, also with the possibility of adding premix(es) in one of the devices. It will be obvious to the skilled man that especially the latter option (several kneading or mixing devices) has numerous drawbacks, if only the necessary space and investment.

(66) Batch modes are preferred and will be referred to here-below.

(67) Routine tests can help the skilled man to select the most appropriate, in view of the available equipment, of the end user practice, and with the help of the following Tables and Figures which are attached to this application.

(68) Tables 1, 2 and 3 and FIGS. 1, 2, 3:

(69) In the tables and FIGS. 1, 2 and 3, a medium filler has been used, that is leading in the cone test, to a diameter of 170 mm with no treating agent (left hand column) and to galette, whose aspect is indicated at the dosage of treating agent equally indicated (dosage is expressed in % by weight of DRY treating agent/CaCO.sub.3 by weight, DRY) after the self-levelling process. As discussed above, 170 mm is by far insufficient.

(70) Table 1 and FIG. 1 correspond to a surface treatment with the superplastifier A described above at a dosage of such as expressed in the corresponding Table.

(71) Table 2 and FIG. 2 correspond to a surface treatment with the superplastifier B described above at a dosage of such as expressed in the corresponding Table.

(72) Table 3 and FIG. 3 correspond to a surface treatment by the product NRG 100 at a dosage such as expressed in the corresponding Table.

(73) TABLE-US-00002 TABLE 1 Medium Filler Test N.sup.o 2312/B 2312/B1 2312/B2 2312/B3 2312/B10 2312/B11 2248/1 2312/B12 2312/B21 Treatment Mode None post ajout post ajout post ajout initial initial initial initial ldige 3 min Treatment Agent None A A A A A A A A Treatment Agent x 0.025% 0.05% 0.5% 0.025% 0.05% 0.1% 0.5% 0.1% dosage - Dosage unit = weight treatment Agent(s) dry/ weight Calcium Carbonate(s) dry Galette = 170 mm 238 mm 306 mm 477 mm 280 mm 308 mm 442 mm 451 mm 435 mm diameter obtained in the self- levelling cone test Result D1 C1 B1 A1 C1 B1 A1 A1 A1 Visual Aspect Plastic Homogeneous Plastic Liquid// Homogeneous Plastic Fluid Fluid Fluid aspect but aspect aspect Fast aspect Aspect do not Spreading spread

(74) TABLE-US-00003 TABLE 2 Medium Filler Test N.sup.o 2312/B 2312/B4 2312/B5 2312/B6 2312/B13 2312/B14 2312/B15 2312/B16 2312/B22 Treatment Mode None post ajout post ajout post ajout initial initial initial initial ldige 5 min Treatment Agent None B B B B B B B A Treatment Agent x 0.025% 0.05% 0.5% 0.025% 0.05% 0.1% 0.5% 0.1% dosage - Dosage unit = weight treatment Agent(s) dry/ weight Calcium Carbonate(s) dry Galette = 170 mm 335 mm 395 mm 457 mm 382 mm 390 mm 425 mm 441 mm 437 mm diameter obtained in the self- levelling cone test Result D1 B1 A1 A1 A1 A1 A1 A1 A1 Visual Aspect Plastic Plastic Fluid Liquid// Fluid Fluid Fluid Fluid Fluid aspect but aspect Fast do not Spreading spread

(75) TABLE-US-00004 TABLE 3 Medium Filler Test N.sup.o 2312/B 2312/B7 2312/B8 2312/B9 2312/B17 2312/B18 2312/B19 2312/B20 2312/B23 Treatment Mode None post ajout post ajout post ajout initial initial initial initial ldige 5 min Treatment Agent None NRG100 NRG100 NRG100 NRG100 NRG100 NRG100 NRG100 NRG100 Treatment Agent x 0.025% 0.05% 0.5% 0.025% 0.05% 0.1% 0.5% 0.1% dosage - Dosage unit = weight treatment Agent(s) dry/ weight Calcium Carbonate(s) dry Galette = 170 mm 220 mm 383 mm 465 mm 328 mm 413 mm 432 mm 451 mm 435 mm diameter obtained in the self- levelling cone test Result D1 C1 A1 A1 B1 A1 A1 A1 A1 Visual Aspect Plastic Homogeneous Fluid Liquid// Plastic Fluid Fluid Fluid Fluid aspect but aspect Fast Aspect do not Spreading spread

(76) In the three curves of FIGS. 1 to 3, the curve corresponding to an addition of the superplastifier(s) AFTER all the other ingredients (COMPARATIVE, MUCH LESS PREFERRED MODE) is marked with diamonds (post ajout mode in the Tables) while the pre-treatment mode or initial (laboratory version of the pre-treatment) curve of the invention is marked with squares (initial mode in the Tables).

(77) The triangle in the Tables is an isolated point corresponding to a 100% pretreatment of the filler in an outside mixing device as for example LODIGUE, during 3 or 5 min., prior to its introduction in the kneading or mixing device (right hand column in the Tables, 435, 437 and 435 mm for the galette in the cone test at only 0.1% dosage).

(78) The said triangle is sometimes difficult to notice on the FIGS. 1-6 because it superimposes with squares and/or diamonds, FIGS. 1 to 6 have been split into FIGS. 1a to 6a (curves) and FIGS. 1b to 6b (schematic, enlarged scale showing the approximate location of the superimposed marks).

(79) It was expected that for treating a coarser filler, the amount of adjuvant(s) must be far or significantly higher. Quite surprisingly, the reverse occurs, that is, proportions such as from 0.03-0.05 to 0.1-0.5% are quite efficient.

(80) We surprisingly note on the curves of FIGS. 1 and 2 (and from the % values in the corresponding Tables 1 and 2) the occurrence of a plateau at about 0.12% so that it is useless to incorporate more that about 0.1% of adjuvant.

(81) The best range is therefore 0.1%-0.12%

(82) To be noted, the study of the lower part of the curves, namely that related to the treatment with B, shows that a clear technical effect appears at 0.03-0.05%: one can note a very steep increase in diameter (consistency) and this represents a threshold dosage (lower limit of the range) that is where the self-levelling (of the galette or cone) requirement of 250-300 mm is reached.

(83) As to table 3 and FIG. 3, one can see that the initial mode curve is quite similar to those of FIGS. 1 and 2, that is a very clear plateau after 0.1-0.12%-0.20% or so, and a similar steep increase in consistency towards the lower dosages, while the post ajout mode curve shows a similar behaviour at the low dosages but (above 0.05% or so) shows a regular but slower increase. For that superplastifier A, one can see that the useful range of dosage in the initial mode process is from 0.05% (corresponds to 300 mm consistency) to 0.1-0.12%-0.20% (beginning of the clear plateau, like in curves 1 and 2); in contrast, with the post ajout mode curve, the lower dosage threshold is about the same (the two curves superpose at about 300 mm) while it is necessary to add about 0.3% of product NRG 100 to reach about 425 mm, vs. about 0.1% for the pre-treatment curve, or the Ldige point.

(84) However, one can see that the initial mode curve allows to reach a plateau at 450 mm for about 0.1-0.12-0.15% of treating agent A used in the process according to the invention, while B and NRG 100 were, for the same % (and for the initial mode curve) at about 425 mm.

(85) One can therefore say that a technical effect appears, depending on the curves and on the desired value of consistency in mm) above 0.02-0.03-0.05% superplastifier(s)/weight cement (dry), at which point that proportion of adjuvant(s) allows the system to be UNblocked; this is the UNblocking point. This unblocking point is probably the key for the unexpected effect of the process of the invention. Therefore, again depending on the adjuvant and on the desired value of consistency, and for THIS filler, one can deduce from the said unblocking point that the optimum proportion is at about 0.08-0.1-0.12-0.15% (since a plateau follows, so that there is no need to add more of expensive adjuvant, for example no need to go up to 0.5%) AND it is most preferable to use a INITIAL MODE or pre-treatment PROCESSthat is the process where the superplastifier(s) adjuvant(s) is/are added with (or at the same point of addition as) the filler (that is, the filler is either first pre-treated with the superplastifier adjuvant in a separate equipment like the known LODIGE mixing device (but with no actual better result, see above the triangle points) or the superplastifier(s) (and optionally the cost-reducing amount of plastifier(s)) is/are added along with the filler since it can be seen from the drawings FIGS. 1, 2 and 3 that the initial mode or pretreatment curve is always better than the post ajout mode curve (that is when the treating agent is added after all the major ingredients including after the filler(s)).

(86) It could even be risky to add more than the optimum 0.1-0.12-0.15% adjuvant/cement since there would be too much of adjuvants and therefore free polymer (that is free adjuvant) would remain in the system. The said excess of adjuvant (free polymer) could interact with cement, with other additives etc. and would be likely to unbalance the system.

(87) Tables 4, 5, 6 and FIG. 4, 5, 6:

(88) The principle and the procedures are the same as in Tables 1-3 and corresponding FIGS. 1-3.

(89) We attach Tables 4, 5 and 6 (corresponding to FIGS. 4, 5 and 6), representing the same trials as above but with a different filler having this time a very good behaviour at the cone test, already 288 mm diameter untreated, and a non-sticky, non-thick and very fluid self-levelled cone or galette.

(90) TABLE-US-00005 TABLE 4 HP Filler Test N.sup.o 2312/A 2312/A1 2312/A2 2312/A3 2312/A10 2312/A11 2239/3b 2312/A17 Treatment Mode None post ajout post ajout post ajout initial initial initial ldige 3 min Treatment Agent None A A A A A A A Treatment Agent x 0.025% 0.05% 0.1% 0.025% 0.05% 0.1% 0.1% dosage - Dosage unit = weight treatment Agent(s) dry/ weight Calcium Carbonate(s) dry Galette = 288 mm 235 mm 361 mm 426 mm 367 mm 400 mm 414 mm 416 mm diameter obtained in the self- levelling cone test Result B1 C1 B1 A1 A1 A1 A1 A1 Visual Aspect Compact// Homogeneous// Plastic Fluid Fluid Fluid Correct Fluid but Sticky Compact aspect Spreading// settles Settles Plastic Aspect

(91) TABLE-US-00006 TABLE 5 HP Filler Test N.sup.o 2312/A 2312/A4 2312/A5 2312/A6 2312/A12 2312/A13 2239/9 2312/A18 Treatment Mode None post ajout post ajout post ajout initial initial initial ldige 3 min Treatment Agent None B B B B B B B Treatment Agent x 0.025% 0.05% 0.1% 0.025% 0.05% 0.1% 0.1% dosage - Dosage unit = weight treatment Agent(s) dry/ weight Calcium Carbonate(s) dry Galette = 288 mm 235 mm 361 mm 426 mm 367 mm 400 mm 414 mm 416 mm diameter obtained in the self- levelling cone test Result B1 D1 B1 A1 A1 A1 A1 A1 Visual Aspect Compact// Slow Plastic Fluid Fluid Fluid but Fluid Fluid but Sticky Spreading aspect settles settles

(92) TABLE-US-00007 TABLE 6 HP Filler Test N.sup.o 2312/A 2312/A7 2312/A8 2312/A9 2312/A14 2312/A15 2312/A16 2312/A19 Treatment Mode None post ajout post ajout post ajout initial initial initial ldige 3 min Treatment Agent None NRG100 NRG100 NRG100 NRG100 NRG100 NRG100 NRG100 Treatment Agent x 0.025% 0.05% 0.1% 0.025% 0.05% 0.1% 0.1% dosage - Dosage unit = weight treatment Agent(s) dry/ weight Calcium Carbonate(s) dry Galette = 288 mm 235 mm 361 mm 426 mm 367 mm 400 mm 414 mm 416 mm diameter obtained in the self- levelling cone test Result B1 C1 A1 A1 A1 A1 A1 A1 Visual Aspect Compact// Homogeneous Correct Fluid// Correct Correct Correct Fluid but Sticky aspect spreading// Compact// Spreading// Spreading// Spreading// settles Compact Settles Compact Compact Compact// Settles

(93) As can be seen, there is a profound difference, for that kind of good or HP filler, between the curves corresponding to the two different processes.

(94) However, it can be seen that for both types of curves there exists an upper optimum limit at about 0.1% superplastifier(s) adjuvant/dry cement, while here-again, adjuvant A behaves slightly differently from B and NRG 100.

(95) As said above, it must however be kept in mind that TWO properties MUST be met simultaneously so as to produce a HP or technical quality system: High consistency that is, roughly speaking, high fluidity/workability as can be seen via the self levelling test, that is diameter above about 250-300 or better above 320-350 mm (and compacity or density that is little porosity) AND SIMULTANEOUSLY a non sticky, not thick (that is, easy to handle), not plastic (and evidently not dry) product, with no decantation.

(96) This can be seen from the above six tables.

(97) For example, in Table 1 and 2 (medium (170 mm) filler+A or B superplastifier), one can see that: tests 2312/B1 and B4, both post ajout mode: with 0.025% of adjuvant, the obtained system is good in diameter (335 mm) only for 2312/B4 though inferior to a dosage at 0.05% (395 mm) BUT B4 forms a non usable product since it has a plastic aspect: the second condition is NOT met, while B5 is fluid and is usable. To the contrary, B1 has an homogeneous aspect at 0.05% but shows only a 238 mm feature, insufficient. tests 2312 B10 (initial that is pretreatment mode) and B13 (initial mode too): for the same dosage, 0.025%, the product B Table 2 leads to a better diameter but above all leads to a fluid product while B10 (forms only an homogeneous product. At the same dosage, B4 with product B leads to a plastic product.

(98) Among the initial mode tests B13 to B16, Table 2, we note that all the systems are fluid, and the difference lies in an increase of the diameter (consistency) with the dosage.

(99) LODIGE: if we compare 2312/B21 (use of a premix in a LODIGE device, at a dosage of 0.1%, and if we compare with an initial mode with no LODIGE, at the same dosage of 0.1%, that is 2248/1 (Table 1), one can see that both are fluid and that the LODIGE brings a slightly lower diameter (435 vs 442 mm) which evidently does not justify the use of the additional equipment LODIGE.

(100) Therefore, the initial or pretreatment mode is best performed by introducing simultaneously the filler(s) and the treatment agent(s) that is at a very close point of addition in terms of location and time.

(101) Each Table and curve can be analysed like above, and the skilled man will be able to use those numerous data, using multiple parameters, different superplastifiers, two different types of filler (one medium at 170 mm consistency, untreated, untreated, the other HP at 280 mm consistency, untreated), and the two process modes, to build his own system in view of the above parameters, his specific needs or requirements.

(102) Mixed-Treatment Test:

(103) A laboratory test has been performed by duplicating test 2248/1 of Table 1 (treatment dosage 0.1%) except that the treatment has been performed on the filler by adding 50% (0.05%) of the efficient amount of superplastifier A to the whole amount of filler (GCC medium quality) and mixing both products in a laboratory mixer, then rapidly introducing the remaining 50% of superplastifier into the kneading or mixing device then introducing 5 s later the filler treated outside by the first 50% of superplastifier A. The diameter in the self levelling test was 392 mm, and the aspect fluid; therefore one can consider that a mixed treatment is slightly inferior in diameter, but is clearly part of the invention.

(104) The whole range of addition of the superplastifier(s) (and optionally of the cost-reducing amount of plastifier(s) can therefore, in view of all the above tests and curves, and general information given in this application, be defined as:

(105) From 0.02-0.03-0.05% to 0.08-0.1-0.12-0.15% adjuvant(s)/dry weight of cement

(106) with easy adjustment by the skilled man.

(107) One can see that all the objectives of the invention, that is the needs and requirements of the MODERN INDUSTRY, are met: at a low dosage (hence at a low cost) of surface treatment by at least one of the adjuvants described above, with no need of using extra equipment, medium to poor behaving fillers (rejected in the prior art or treated at unreasonable costs and investments) can be easily upgraded to HP fillers capable of forming with the other usual ingredients cement or mortar or concrete compositions or systems which are of the technical grade, with a High to very High consistency, above 250, 300, or even above 350 mm in the self levelling standardized test, a High to very High compacity (density), a high to very high % of dry material in the end product, from 87 to 95%, by weight, of dry material in the final, complete system. what provides the skilled man not only with the possibility of meeting the most stringent and recent industrial requisites, but also to obtain products featuring for the first time a regularity in the properties, that is predictability.

(108) That regularity is a novel property which was not reached by far in the prior art, despite the demand by the industry; it is believed, without being tied by a theory, that the process steps and the used superplastifiers are responsible for this regularity.

(109) The follow-up of the regularity is possible by adjusting the dosage of the A and B above surface-treatment products, or by selecting other products as described hereabove, and adjusting the dosage, using the above described test method to ensure that the properties remain constant, what is called regularity.

Application(s)

(110) The applications are all those commonly using the above described cement, mortar, or concrete compositions or systems.

Cement Products

(111) Those are the products or elements that are known to be manufactured from the above cement, mortar or concrete compositions, in the building industry or any other industry, in a well-known manner.