CALCIUM ALUMINATE CEMENT WITH LONG OUVABILITY AND HARDENING PROMOTED BY TEMPERATURE ELEVATION, AND U

专利摘要:
The invention relates to a calcium aluminate cement, comprising a calcium aluminate with a first crystalline mineral phase of calcium bialuminate CA2 comprising a calcium oxide CaO for two aluminum oxides Al2O3 and / or a second crystallized mineralogical phase of C2AS bicalcium alumina silicate comprising two calcium oxides CaO for an aluminum oxide Al2O3 and a silicon dioxide SiO2 According to the invention, the mass fraction of all of said first and second mineralogical phases in said calcium aluminate is greater than or equal to 80%.
公开号:FR3039538A1
申请号:FR1557167
申请日:2015-07-27
公开日:2017-02-03
发明作者:Bruno Espinosa；Mark Winslow Fitzgerald；Charles Walter Alt；Philippe Thouilleux；Ratana Soth；Michaël Lievin
申请人:Kerneos SA；
IPC主号:

专利说明:

La ligne LOI à savoir Loss on gnition, ou Perte au feu, regroupe ici les éléments volatils tels que l’humidité résiduelle dans le cas de la bauxite ou le dioxyde de carbone C02 dans le cas du calcaire.
Le tableau 1 ci-dessous donne les phases minéralogiques contenues dans ces premier, deuxième et troisième ciments (Cimentl, Ciment2, Ciment3).
Tableau 1 :
La notation na signifie que le ciment ne comprend pas la phase minéralogique correspondante.
La phase minéralogique Ferrites comprend essentiellement la phase minéralogique de Ferro-aluminate tétra-calcique C4AF, appelée dans la suite sixième phase minéralogique cristallisée. La maille cristalline de cette sixième phase minéralogique cristallisée comprend quatre molécules de chaux C pour une molécule d’alumine A et un oxyde de fer Fe2Û3, abrégé par la lettre F.
La colonne « autres » regroupe les impuretés comprises dans ces ciments, à savoir au moins un des composés suivant : oxyde de fer Fe203, oxyde de titane TiOo. oxvde de soufre SOs. oxvde de maanésium MaO. et des comoosés
alcalins.
Un quatrième ciment (Ciment4) a également été utilisé en comparaison des trois ciments d’aluminates de calcium Cimentl, Ciment2, Ciment3.
Ce quatrième ciment Ciment4 est un ciment Portland de classe G classiquement connu de l’homme du métier et souvent utilisé dans des applications de type forage pétrolier. 2/ Temps d’épaississement
Un premier test ayant permis de caractériser les ciments étudiés a consisté à mesurer le temps d’épaississement de différentes compositions cimentaires obtenues en mélangeant ces ciments avec de l’eau.
Le temps d’épaississement est une donnée permettant d’apprécier l’ouvrabilité de la composition cimentaire, en particulier lorsqu’elle se présente sous forme d’une suspension aqueuse.
Au sens où on l’entend ici, le temps d’épaississement est une estimation de la durée au bout de laquelle la composition cimentaire ne peut plus être pompée. Autrement dit, il s’agit de la durée au bout de laquelle une suspension aqueuse est trop visqueuse pour pouvoir être déplacée au moyen d’une pompe.
Plus précisément, le temps d’épaississement correspond à la durée qui s’est écoulée entre le moment où l’eau et le ciment ont été mélangés pour former la composition cimentaire sous forme de suspension aqueuse, et le moment où la consistance, dite consistance Bearden (Bc), de la composition cimentaire a atteint une valeur telle que cette composition cimentaire ne peut plus être pompée, la consistance Bearden étant exprimée au moyen d’une grandeur sans unité.
Ici, la mesure du temps d’épaississement se fait selon la norme ISO 14026-1, clause 10.3, et le temps d’épaississement est tel que la composition cimentaire a atteint une consistance Bearden de 100 Bc, à 23°C, sous pression atmosphérique de 1 atmosphère (atm).
En pratique, la mesure de ce temps d’épaississement s’effectue par exemple au moyen d’une pale de brassage adaptée à tourner dans la composition cimentaire tout en mesurant un couple. Ce couple mesuré permet d’apprécier la force que la pale doit exercer sur la composition cimentaire pour pouvoir tourner. Ce couple est ainsi relié à la consistance Bearden de la composition cimentaire.
Le tableau 2 ci-dessous présente différentes compositions cimentaires qui ont été formées à partir des trois ciments d’aluminates de calcium Cimentl,
Ciment2, Ciment3, et du ciment Portland Ciment4, ainsi que le temps d’épaississement qui leur est associé, à température ambiante (23°C).
Dans ce tableau 2, le ratio eau/ciment représente la masse d’eau qui a été introduite pour former la composition cimentaire, par rapport à la masse de ciment sèche.
Tableau 2 :
Dans le tableau 2, on peut voir que les compositions cimentaires Compol et Compo2 formées à partir des ciments d’aluminates de calcium de l’art antérieur Cimentl et Ciment2 présentent des temps d’épaississement relativement courts (inférieurs à 2 heures) à température ambiante (23°C). Si l’utilisateur a besoin d’un temps supérieur à ces temps d’épaississement pour pouvoir utiliser les compositions cimentaires comprenant les deux ciments Cimentl et Ciment2, il devra leur ajouter des retardateurs de prise.
La composition cimentaire Compo4 comprenant le Ciment4 confirme que les ciments Portland présentent un temps d’épaississement moyen (autour de 5 heures) à température ambiante (23°C). C’est pouquoi ces ciments sont souvent utilisés dans les applications nécessitant un temps de mise en œuvre assez long.
La composition cimentaire Compo3 comprenant le ciment d’aluminate de calcium selon l’invention Ciment3 présente un temps d’épaississement supérieur à 10 heures, ce qui offre la possibilité à l’utilisateur d’utiliser - par exemple de transporter, de couler, d’injecter, de pomper, etc. - cette composition cimentaire Compo3 pendant un temps long, et ce sans avoir à y ajouter de retardateur.
En outre, elle présente un temps d’épaississement près de deux fois supérieur à celui de la composition cimentaire Compo4 à température ambiante (23°C), alors même qu’elle comprend moins d’eau et devrait donc être plus réactive aue la comoosition cimentaire Comoo4.
Le ciment selon l’invention Ciment3 présente donc une ouvrabilité très grande sans ajout de retardateur de prise. Ainsi, il convient particulièrement aux applications nécessitant un temps ouvert très long, et cela sans pollution chimique liée à l’utilisation de retardateurs de prise. 3/ Viscosité
Un deuxième test ayant permis de caractériser les ciments étudiés a consisté à mesurer la viscosité de certaines compositions cimentaires.
La viscosité permet d’apprécier la cinétique de durcissement et l’ouvrabilité de ces compositions cimentaires.
Il s’agit ici de mesurer la rhéologie des compositions cimentaires, c’est-à-dire leur aptitude à s’écouler et/ou à se déformer.
Au sens où on l’entend ici, la mesure de la viscosité se fait selon la norme ISO 14026-2, clause 12.
Plus précisément, la mise en oeuvre du test de viscosité se fait comme suit : le ciment est mélangé à la quantité choisie d’eau pour former la composition cimentaire, puis cette composition cimentaire est placée sur un viscosimètre rotatif de la marque FANN® 35.
La rhéologie de la composition cimentaire est alors testée directement après le mélange entre le ciment et l’eau (Viscosité initiale V1), ou après une période de repos de 10 minutes (Viscosité V2), à une température de 23°C, de 50°C ou de 80°C et à pression atmosphérique de 1 artnosphère (atm) environ, pour une vitesse de rotation du viscosimètre de 3 tours par minute (rpm).
Le tableau 3 ci-dessous présente les différentes compositions cimentaires testées et leur viscosité respective V1 et V2 à 23°C, le tableau 4 présente des compositions cimentaires similaires et leur viscosité à 50°C, et le tableau 5 présente les mêmes compositions cimentaires que celles du tableau 4 et leurs viscosités à 80°C.
Dans ces trois tableaux 3, 4 et 5, les compositions cimentaires testées dépendent à la fois du ciment utilisé, de la surface spécifique Blaine choisie pour le ciment, et du ratio eau/ciment choisi.
Tableau 3
Ainsi, la composition cimentaire Compo5 comprenant le ciment d’aluminate de calcium de l’art antérieur Ciment2 présente une viscosité initiale V1 acceptable pour pouvoir être manipulée, mais sa viscosité après 10 minutes est celle d’une composition cimentaire gélifiée. Par conséquent, dès que la composition cimentaire Compo5 est laissée immobile trop longtemps, elle ne peut plus être manipulée. Cela est particulièrement gênant lorsqu’on souhaite déplacer une telle composition cimentaire au moyen de pompes, qui risqueraient alors d’être endommagées dès leur arrêt.
En revanche, les compositions cimentaires selon l’invention Compo6 à CompolO sont particulièrement avantageuses dans la mesure où leurs viscosités initiale V1 sont faibles (inférieures à 20), ce qui facilite leur transport au moyen de pompe. Leur viscosité V2 après un temps de pause reste également suffisamment faible pour que l’on puisse les pomper.
Ainsi, la cinétique de durcissement des compositions cimentaires comprenant le ciment d’aluminates de calcium selon l’invention Ciment3 est bien plus lente que celles des compositions cimentaires de l’art antérieur, ce qui est un avantage pour des utilisations nécessitant une longue manipulation.
En outre, le tableau 3 donne également une indication de la réactivité du ciment d’aluminates de calcium Ciment3 selon l’invention en fonction de la surface spécifique Blaine. On remarque en effet que plus la surface spécifique Blaine augmente, plus la viscosité initiale et la viscosité après pause augmentent. Ainsi, la cinétique de durcissement accélère lorsque la surface spécifique Blaine
augmente, ce qui traduit le fait que les grains de poudre les plus fins sont plus facilement hydratés par l’eau car ils présentent une plus grande surface réactive.
Tableau 4
En comparant les tableaux 3 et 4, on constate que la viscosité initiale de la composition cimentaire Compo11 du tableau 4 comprenant le ciment d’aluminates de calcium de l’art antérieur Ciment2 augmente lorsque la température augmente, alors même qu’elle comprend plus d’eau que la composition cimentaire similaire Compo5 du tableau 3.
En outre, comme dans le cas de la composition cimentaire Compo5, la viscosité V2 après pause de la composition cimentaire Compol 1 est également trop importante pour que cette composition cimentaire Compol 1 puisse être utilisée dans des pompes sans lui ajouter de retardateur de prise.
Par ailleurs, les compositions cimentaires selon l’invention Compol 2 à Compol 4 présentent des viscosités initiales V1 faibles et des viscosités V2 après un temps de pause permettant encore leur utilisation ainsi que leur transport au moyen de pompes.
En outre, à cette température (50°C), la surface spécifique Blaine joue un rôle important sur la viscosité : plus la surface spécifique Blaine augmente, plus la viscosité augmente.
Tableau 5
Le tableau 5 montre qu’à 80°C, la composition cimertaire Compo11 comprenant le ciment d’aluminate de calcium de l’art antérieur Ciment2 ne peut pas être utilisée car sa viscosité est trop importante dès le mélange avec l’eau.
La viscosité initiale V1 des compositions cimentaires comprenant le ciment selon l’invention Ciment3 à 80°C est du même ordre de grandeur qu’à 50 °C.
Par contre, l’élévation de température influence la viscosité V2 après un temps de pause des compositions cimentaires Compo12 à Compo14. En effet, la viscosité après pause augmente nettement entre 50°Cet 80°C, et d’autant plus si la surface spécifique Blaine est grande. Cela confirme le fait que la température favorise la réaction entre l’eau et le ciment selon l’invention Ciment3. 4/ Résistance mécanique D’autre part, il est également possible d’apprécier la cinétique de durcissement des compositions cimentaires en mesurant la résistance mécanique atteinte par le matériau final durci obtenu après réaction entre l’eau et le ciment.
En pratique, on forme la composition cimentaire en mélangeant l’eau et le ciment, puis on laisse la composition cimentaire reposer pendant 24 heures, à une température choisie et une pression choisie, avant de mesurer la résistance mécanique selon la norme ISO 14026-1, clause 9.2.
Le tableau 6 présente les résistances mécaniques des trois compositions cimentaires Compol, Compo2 et Compo3 après 24 heures à 37°C et sous pression atmosphérique (R1), après 24 heures à 60°C et sous pression atmosphérique (R2), et après 24 heures à 110°C et sous pression de 20,7 MégaPascal (R3).
Les résistances mécaniques R1, R2 et R3 sont données en MégaPascal (MPa).
Tableau 6
Dès 37°C, la résistance mécanique développée par les compositions cimentaires Compol et Compo2 comprenant les ciments d’aluminates de calcium selon l’art antérieur Cimentl et Ciment2 est importante, ce qui confirme le fait que ces compositions cimentaires Compol et Compo2 réagissent à faible température.
Au contraire, la composition cimentaire Compo3 comprenant le ciment selon l’invention Ciment3 présente une résistance mécanique nulle à 37°C, et quasi-nulle à 60°C, ce qui indique que ce ciment nëst que très peu réactif en dessous de 60°C. Ainsi, cela conforte le fait que b réaction du ciment selon l’invention avec l’eau est naturellement retardée à des températures inférieures à 60°C, sans avoir besoin d’y ajouter de retardateur.
Après 24 heures à 110°C, les résistances mécaniquesdes compositions cimentaires Compol et Compo2 sont plus élevées, ce qui prouve que ces compositions cimentaires réagissent plus rapidement à cette température qu’à une température de 37°C. A 110°C, la composition cimentaire Compo3 développe également une résistance mécanique de l’ordre d’une vingtaine de mégaPascals. Ainsi, la réaction entre le ciment selon l’invention et l’eau est favorisée par des hautes températures.
Par conséquent, le ciment d’aluminates de calcium selon l’invention présente une cinétique de durcissement naturellement contrôlée par la température, sans avoir besoin d’ajouter de retardateur.
En outre, à 110°C, la résistance mécanique R3 dévebppée par la composition cimentaire Compo3 comprenant le ciment d’aluminates de calcium selon l’invention Ciment3 est similaire à celle des ciments d’aluminates de calcium usuellement utilisés et connus à ce jour (de l’ordre de 20 MPa). 5/ Temps de prise et contamination
Un autre test a oorté sur l’effet de la contamination d’un ciment Portland
par un ciment selon l’invention. A cet effet, on a mesuré le temps de prise de différentes compositions cimentaires comprenant à la fois un ciment Portland et un ciment d’aluminates de calcium.
Au sens où on l‘entend ici, le temps de prise est mesuré selon la norme ASTM C91, à l’aide d’une aiguille de Vicat.
Le test de Vicat consiste à mélanger l’eau et le ciment pour former la composition cimentaire, puis à laisser tomber une aiguille de Vicat dans la composition cimentaire, qui est statique, à intervalle de temps régulier. Tant que l’aiguille s’enfonce jusqu’au fond de la composition cimentaire, on considère que le temps de prise n’est pas atteint, dès qu’elle s’enfonce sans pouvoir aller jusqu’au fond de la composition cimentaire, on a atteint le temps de prise.
En pratique, le temps de prise correspond donc à la durée qui s’est écoulée entre le moment où le ciment et l’eau ont été mélangés pour former la composition cimentaire dans un état liquide, et le moment où la composition cimentaire est passée dans un état suffisamment solide pour que l’aiguille de Vicat ne puisse plus la traverser entièrement mais seulement partiellement, à une température de 23 °C et sous pression atmosphérique(1atm).
Le tableau 7 ci-dessous présente les temps de prise, en minutes, de différentes compositions cimentaires comprenant une certaine proportion de ciment d’aluminates de calcium mélangée à un ciment Portland. Le ciment Portland utilisé est un ciment Portland de classe H.
Dans ce tableau 7, les pourcentages donnent la masse de ciment d’aluminates de calcium ajoutée par rapport à la masse totale sèche de ciment utilisé. Ainsi, le complément pour atteindre 100% correspond à la masse de ciment Portland contenue dans la masse totale sèche de ciment.
Le ratio eau/ciment est de 0,38, c’est-à-dire que la masse d’eau utilisée représente 38% de la masse totale sèche de ciment utilisé.
Tableau 7
Le tableau 7 présente l’effet sur le temps de prise de la contamination d’un ciment Portland par un ciment d’aluminates de calcium. D’après le tableau 7, les ciments d’aluminates de calcium de l’art antérieur Cimentl et Ciment2 ont un effet conséquent sur le temps de prise du ciment Portland utilisé. En effet, alors que le ciment Portland seul, correspondant à la première colonne, présente un temps de prise relativement long de 400 minutes, le temps de prise observé pour un mélange avec 15% de ciment d’aluminates de calcium Ciment et Ciment2 est très court (10 et 20 minutes). Cela signifie qu’une composition cimentaire contenant un ciment Portland et un ciment d’aluminates de calcium de l’art antérieur réagit de façon ultra rapide, empêchant l’utilisation d’une telle composition cimentaire pour des applications nécessitant des mises en oeuvre longues. De telles compositions cimentaires ne peuvent donc pas être utilisées dans des applications de type puits de forage par exemple.
En revanche, la contamination du ciment Portland par le ciment selon l’invention Ciment3 n’a que peu d’effet, à température ambiante, sur le temps de prise de la composition cimentaire. En effet, le temps de prise d’une composition cimentaire comprenant 15% de Ciment3 et 85% de ciment Portland correspond à 75% du temps de prise d’une composition cimentaire comprenant 100% de ciment Portland.
Par conséquent, l’utilisation du ciment d’aluminates de calcium selon l’invention Ciment3 est facilitée par rapport aux autres ciments d’aluminates de calcium dans la mesure où il n’est pas nécessaire de nettoyer les installations avant de pouvoir utiliser ces installations pour un ciment Portland. 6/ Degré d’hydratation
Un dernier test a consisté à évaluer l’influence de la température sur le dearé d’hvdratation du ciment selon l’invention Ciment3.
Ce test se base sur des observations au microscope à balayage électronique permettant une quantification selon la méthode Rietvled ainsi que sur des mesures de diffractions aux rayons X.
En pratique, une composition cimentaire Compo15 a été formée en mélangeant de l’eau avec le ciment selon l’invention Ciment3 dans un ratio eau/ciment de 0,44, c’est-à-dire de sorte que l’eau représente 44% en masse par rapport à la masse totale sèche de ciment.
On a également formé une composition cimentaire Compo16 en mélangeant de l’eau avec le ciment de l’art antérieur Ciment2 dans un ratio eau/ciment de 0,44.
Ces compositions cimentaires Compo15 et Compo16 ont ensuite été soumises à un test de diffraction aux rayons X dès qu’elles ont été formées (D1), après un repos à 23°C (D2) pendant 24 heures, après un passage à l’autoclave pendant 24 heures à 120°C (D3), et après un passage à l’autoclave pendant 24 heures à 180°C (D4).
Les résultats de ce test de diffraction aux rayons X permettent d’estimer le pourcentage de chaque phase minéralogique présente dans les compositions cimentaires Compo15 et Compo16 ainsi que l’eau libre restante, en masse par rapport à la masse totale de la composition cimentaire Compol 5, en fonction du traitement qu’elles ont subi.
Les résultats permettent également d’estimer le pourcentage d’hydrates formés pendant la réaction d’hydratation de l’eau avec les ciments Ciment3 et Ciment2, en fonction des différents traitements subis. Les hydrates sont des composés formés entre l’eau (notée H) et les composés chimiques hydratés issus des phases minéralogiques comprises initialement dans les ciments étudiés.
Autrement dit, les résultats du test de diffraction aux rayons X permettent d’estimer le degré d’hydratation des phases minéralogiques du ciment selon l’invention Ciment3 ou du ciment de l’art antérieur Ciment2, en fonction de la température.
On entend par « eau libre », l’eau qui n’est pas engagée dans des liaisons avec des ions provenant des différentes phases minéralogiques hydratées, c’est-à-dire qui n’appartient pas déjà à un hydrate formé. Autrement dit, il s’agit de l’eau encore disponible pour hydrater les phases minéralogiques encore existantes.
Dans les tableaux 8 et 9, la phase « autres >> regroupe les impuretés éventuelles (oxyde de fer Fe2Ü3, oxyde de titane T1O2, oxyde de soufre SO3, oxyde de magnésium MgO, et des composés alcalins).
Le tableau 8 ci-dessous présente les résultats du test de diffraction aux rayons X, à savoir le pourcentage de chaque phase minéralogique et de chaque hydrate présent après chaque traitement subi par la composition cimentaire Compo15.
Le tableau 9 présente quant à lui les résultats du test de diffraction aux rayons X, après chaque traitement subi par la composition cimentaire Compo16.
Tableau 8
Dans ce tableau 8, la phase « autres >> comprend également la phase CA. Cette phase CA est présente initialement lors du mélange entre le ciment3 et l’eau (colonne D1), et est absente du mélange après 24 heures de réaction (colonnes D2, D3 et D4) car elle a totalement réagi avec l’eau, quelle que soit la température.
Comme le montre le tableau 8, les première et deuxième phases minéralogiques CA2, C2AS réagissent peu, voire pas, en dessous de 120°C.
Par contre, la première phase minéralogique CA2 réagit entièrement dès 120°C. Autrement dit, à partir de 120°C, la premièe phase minéralogique CA2 est entièrement hydratée par l’eau.
La deuxième phase minéralogique C2AS réagit à partir de 120°C, mais elle est moins réactive que la première phase minéralogique CA2.
Ainsi, la réactivité de la première phase minéralogique CA2 est favorisée par une température inférieure à celle favorisant la réactivité de la deuxième phase minéralogique C2AS.
Tableau 9
En comparant les tableaux 8 et 9, on remarque que les hydrates C3AH6, AH3, et AH formés par la réaction d’hydratation du ciment d’aluminate de calcium de l’art antérieur Ciment2 avec l’eau sont également formés par la réaction d’hydratation du ciment d’aluminates de calcium selon l’invention Ciment3 avec l’eau.
En outre, lors de la réaction d’hydratation du ciment d’aluminates de calcium selon l’invention Ciment3 avec l’eau, un hydrate supplémentaire C3AS(3-x)H4x est également formé.
Ainsi, la présence des mêmes hydrates dans le matériau final durci obtenu à partir du ciment d’aluminates de calcium de l’art antérieur Ciment2 et dans le matériau final durci obtenu à partir du ciment d’aluminates de calcium selon l’invention Ciment3 montre que les propriétés de résistance chimique de ces matériaux finaux durcis sont similaires.
Par conséquent, le ciment selon l’invention présente des propriétés de résistance chimique similaires à celles des ciments d’aluminates de calcium déjà connus.
Ainsi, l’ensemble des expériences effectuées montrent que le ciment d’aluminates de calcium selon l’invention présente une cinétique de durcissement lente à température ambiante, ce qui permet de l’utiliser sans retardateur de prise.
Cette cinétique de durcissement peut être ajustée en fonction de la température et en choisissant la proportion relative de première et de deuxième
phase minéralogique CA2, C2AS.
En outre, à température ambiante, le ciment d’aluminates de calcium selon l’invention présente un faible pouvoir contaminant sur les ciments Portland.
Enfin, les propriétés mécaniques du matériau final durci obtenu à partir du ciment d’aluminates de calcium selon l’invention sont semblables à celles des matériaux finaux durcis obtenus à partir des ciments d’aluminates de calcium connus.
Technical field to which the invention relates
The present invention generally relates to the field of cements whose hardening in the presence of water is favored by a rise in temperature.
It relates in particular to a calcium aluminate cement comprising a calcium aluminate with a first crystallized mineral phase of calcium bialuminate Ca2 comprising a calcium oxide CaO for two aluminum oxides Al203 and / or a second crystallized mineral phase of silicate of C2AS bicalcium alumina comprising two CaO calcium oxides for an Al 2 O 3 aluminum oxide and SiO 2 silicon dioxide.
It also relates to a cementitious composition comprising such a calcium aluminate cement, mixed with water and optionally with other compounds such as fly ash, a granulated blast furnace slag, a silica flour, silica fume, metakaolin, quartz, fine limestone, sand, and admixtures. The invention finds a particularly advantageous application in any application where a rise in temperature is necessary or undergone, such as for example the consolidation of oil wells.
Technological background
A cement is a mineral powder adapted to be mixed with water to form a paste-like or liquid-consistency cementitious composition which hardens to form a cured final material.
There are many cements on the market that are distinguished, on the one hand, by their reactive properties with water, and on the other hand, by the mechanical and chemical properties of the hardened final materials that they achieve.
For example, calcium aluminate cements provide the cured end materials with specific chemical properties of high resistance to acid corrosion and high strength mechanical properties at high temperatures and pressures.
The reactive properties of a cement when mixed with water determine the workability of the cementitious composition formed by the mixing of this cement with water, that is to say the duration, also called " open time >>, during which this cementitious composition has a viscosity adapted to its use, namely, for example, a low viscosity to allow its injection into cracks, or a moderate viscosity to allow its forming in formwork.
These reactive properties also determine the kinetics of hardening of the cementitious composition during subsequent phases of the reaction of cement with water. These include the characteristics of the hydraulic setting of the cementitious composition, the hydraulic setting being an accelerated exothermic phase of the hydration reaction of the cement by the water, and the rate at which the final hardening of the material occurs. after the hydraulic setting, ie how long the cured final material achieves a desired mechanical strength. On the other hand, it is known that a relatively high temperature, that is to say higher than about 50 ° C, can accelerate the kinetics of hardening of a cementitious composition, and substantially reduce its workability including promoting thickening of the cementitious composition and triggering the hydraulic setting more quickly.
To reduce the effect of temperature on the reactivity of cementitious compositions, it is common to add adjuvants to cementitious compositions, such as setting retarders.
However, since several retarders can be used in the same cementitious composition, these retarders can interact with each other and / or with the other additives of the cementitious composition, and it becomes difficult to predict the kinetics of hardening of this cementitious composition.
In addition, the presence of a retarder in the cementitious composition can lead to a lowering of the mechanical strength of the cured final material.
In addition, it is also known that, because of these problems of workability and kinetics of hardening, the cementitious compositions are generally manufactured on site, that is to say that the water is added to the cement directly on the surface. place of use of the cement compositions.
It thus happens regularly that, on site, cementitious compositions based on calcium aluminate cements are prepared in the production lines usually used to prepare the cementitious compositions based on Portland cement.
Since production lines have dead zones that are difficult to purge and / or clean, there may be some cement left from one production season to another. Thus, during the preparation of a Portland cement-based cementitious composition, this Portland cement may have been polluted by calcium aluminate cement residues, or vice versa.
However, it turns out that Portland cements and calcium aluminate cements interact with each other, and that this interaction accelerates the kinetics of hardening of the cement compositions obtained. Thus, the hydraulic setting of a cementitious composition based on a mixture of Portland cement and calcium aluminate cement is initiated earlier than expected for a cementitious composition based on Portland cement or cement. calcium aluminates only. When this mixture results from an involuntary pollution, the acceleration of setting can lead to a blockage of the installations, which is very problematic.
An application in which generally involve high temperatures, and for which it is essential to control the workability and hardening kinetics of the cementitious compositions formed is the consolidation of the wells.
The drilling of wells, particularly oil wells, is a complex process that consists mainly of drilling the rock while introducing a tubular metal body.
It is known to cement the walls of the wellbore both to reinforce the formwork of these wells, to protect the tubular body inserted therein from corrosion, and to seal this tubular body in the surrounding rock.
To do this, manufacturers use cementitious compositions in the form of aqueous suspensions commonly called "slurry", mainly comprising a cement dispersed in a large amount of water, which they inject into the tubular body to the bottom of it. this. The aqueous suspension then rises towards the surface, in the space existing between the rock wall and the tubular body.
It is then understood that the workability of the aqueous suspension must be such that this aqueous suspension can be injected to the bottom of the tubular body, and that the hydraulic setting of the aqueous suspension must occur at a controlled moment after the ascent to the surface of this aqueous suspension, taking into account the subterranean conditions of high temperatures and pressures.
For example, document US20130299170 discloses complex cement compositions in the form of aqueous suspensions, suitable for the consolidation of oil wellbores, which comprise calcium aluminate cements and setting retarders comprising an organic acid and a mixture of polymers. .
Documents US6143069 and US20040255822 also disclose cementitious compositions in the form of low density aqueous suspension suitable for the consolidation of oil wells, comprising commercial calcium aluminate, SECAR-60 ™ or REFCON ™ brand, ashes. aerosols, water, retarders such as citric, gluconic or tartaric acids and other additives such as foaming agents and agents preventing loss of fluid.
However, the cementitious compositions thus formulated to reduce the effect of temperature on their workability and curing kinetics are particularly complex. They also cause the use of many different chemical compounds, which can have an adverse effect on the environment.
There is therefore a need to be able to benefit from the properties provided by the hydration of calcium aluminates while controlling the workability period more easily, especially when the temperature is high.
Object of the invention
In order to overcome the aforementioned drawbacks of the state of the art, the present invention proposes a novel calcium aluminate cement, which has the advantageous properties of chemical resistance and mechanical strength of this type of cement, as well as a time naturally long open without addition of retarder, and even in case of involuntary mixing with Portland cements.
More particularly, it is proposed according to the invention a calcium aluminate cement as described in the introduction, wherein the mass fraction of all of said first and second mineralogical phases in said calcium aluminate is greater than or equal to 80%.
Thus, thanks to these crystallized mineralogical phases, the calcium aluminate cement according to the invention has a controlled curing kinetics, without the need to add a retarder.
More specifically, the Applicant has found that the calcium aluminate cements comprising these mineralogical phases exhibited, at ambient temperature, an extremely long workability, and that the reactivity of these phases with water was favored by a rise in temperature. Thus, at room temperature, the reactivity of the calcium aluminate cement according to the invention with water is low and the kinetics of the hydration reaction is very slow. The workability of the cementitious composition based on this cement is thus controlled without the addition of retarding agents in the form of additional chemical compounds.
In addition, the kinetics of curing is controlled because the hydraulic setting can be triggered and / or accelerated by a rise in temperature.
In addition, these mineralogical phases guarantee the calcium aluminate cement according to the invention reduced interactions with Portland cements, which reduces the problems associated with cross-contamination between Portland cements and calcium aluminate cements.
Finally, the calcium aluminate cement according to the invention has high strength and high pressure strength properties, and chemical corrosion resistance to acids similar to those of calcium aluminate cements already known in the art. 'state of the art. Other nonlimiting and advantageous characteristics of the calcium aluminate cement according to the invention, taken individually or in any technically possible combination, are the following: said calcium aluminate also comprises an amorphous part, the mass fraction of which in said calcium aluminate is less than or equal to 20%; said calcium aluminate further comprises a third crystallized mineralogical phase of monocalcium aluminate CA comprising a calcium oxide CaO for an aluminum oxide Al203 and / or a fourth crystallized mineral phase calcium hexaaluminate CA6 comprising a calcium oxide CaO for six aluminum oxides AI2O3, the mass fraction of all the third and fourth mineralogical phases in said calcium aluminate being less than or equal to 20%; it comprises, by weight relative to the total mass of said calcium aluminate: 0% to 5% iron oxide Fe2O3, 0% to 5% titanium oxide T1O2, 0% to 5% sulfur oxide SO3, 0% to 5% magnesium oxide MgO, 0% to 2% alkaline compounds; it is in the form of a powder having a Blaine specific surface area measured according to the NF-EN-196-6 standard of between 2200 square centimeters per gram and 4500 square centimeters per gram, preferably between 2900 and 3900 square centimeters per square centimeter; gram; it comprises, by weight relative to the total mass of said calcium aluminate: 50% to 60% of the first crystallized mineral phase CA2, 26% to 32% of the second crystallized mineral phase C2AS, 2.5% to 3.5% crystallized third CA mineral phase, 0.5% to 1.5% of a fifth crystallized mineralogical phase of C4AF tetracalcium ferroaluminate, 10% to 15% additional crystalline mineralogical phases. The invention also proposes a cementitious composition comprising at least the calcium aluminate cement according to the invention mixed with water, and optionally cementitious additives such as fly ash and / or granulated blast furnace slag and / or silica flour and / or silica fume and / or metakaolin, aggregates such as quartz and / or fine limestone and / or sand, and adjuvants. The invention also proposes a use of the calcium aluminate cement as described above, according to which a) a cementitious composition is produced by mixing at least said calcium aluminate cement with water, b) placing said cementitious composition, c) heating said cementitious composition at a temperature between 50 ° C and 300 ° C, preferably between 80 ° C and 20 ° C, so as to promote the setting of the cementitious composition.
In particular, this use of calcium aluminate cement finds a particularly advantageous application in the consolidation of boreholes, including oil wells.
For this, in step a) of the use according to the invention, the cementitious composition is in the form of an aqueous suspension, and in step b), the cementitious composition is placed in a wellbore oil.
Detailed description of an example of realization
The following description with reference to the accompanying drawings, given as non-limiting examples, will make it clear what the invention consists of and how it can be achieved.
In the accompanying drawings: FIG. 1 is a lime-alumina-silica ternary diagram, represented as a mass fraction of lime, alumina and silica; - Figure 2 is a zoom of Figure 1 in the area of interest [ll-ll] to describe the composition range of calcium aluminate according to the invention.
For the purposes of the invention, and unless otherwise specified, the indication of an interval of values "X to Y" or "between X and Y" in the present invention means as including the X and Y values.
The present invention relates to a calcium aluminate cement adapted to be mixed with water to form a cementitious composition whose workability is naturally long, and whose reactivity is favored by a rise in temperature.
In the remainder of the description, the term "cement" will mean a powder adapted to be mixed with water to form a cementitious composition capable of hardening to form a hard final material.
The term "cementitious composition" will mean mixing the cement with water and possibly with other additional compounds.
Finally, as will be well explained later, the "reactivity" or "reactive properties" of cement characterize the ability of this cement to react with water. From a chemical point of view, the calcium aluminate cement according to the invention comprises at least one calcium aluminate, that is to say a compound comprising both a calcium oxide and an aluminum oxide. .
More specifically, here, the calcium aluminate of the cement according to the invention comprises a calcium oxide commonly called lime CaO, an aluminum oxide commonly called alumina Al2O3, and a silicon dioxide commonly called silica S102.
In order to lighten the notations, as classically do cementists in their notations, we will abbreviate thereafter lime CaO by the letter C, the alumina AI2O3 by the letter A and the silica S1O2 by the letter S.
These three compounds, namely lime C, alumina A and silica S, are the major compounds present in the calcium aluminate according to the invention. The calcium aluminate according to the invention may also comprise, by weight relative to the total mass of said calcium aluminate: - 0% to 5% of an iron oxide Fe2O3, - 0% to 5% of an oxide titanium TiO2, 0% to 5% sulfur oxide SO3, 0% to 5% magnesium oxide MgO, 0% to 2% alkaline compounds.
These other compounds are minor in the calcium aluminate of the cement according to the invention. They are impurities that generally come from the raw materials used for the production of calcium aluminate. From a mineralogical point of view, the calcium aluminate cement according to the invention comprises a crystalline part and an amorphous part.
These crystalline and amorphous parts characterize the microscopic state of the calcium aluminate cement according to the invention: the crystalline part of this calcium aluminate cement comprises atoms and / or molecules ordered according to a particular geometry, in crystallized mineralogical phases , while the amorphous part of this calcium aluminate cement comprises atoms and / or molecules which are arranged in a disordered manner with respect to each other, that is to say in no particular order.
Here, the calcium aluminate of the cement according to the invention is mainly crystalline.
More specifically, advantageously, in the calcium aluminate cement according to the invention, the mass fraction of said crystalline part in said calcium aluminate is greater than or equal to 80%.
In other words, the mass of the crystalline part relative to the total mass of the calcium aluminate of the cement according to the invention is greater than or equal to 80%.
Thus, in the calcium aluminate cement according to the invention, the mass fraction of the amorphous part is less than or equal to 20%.
The crystalline part has crystallized mineralogical phases which make it possible more specifically to describe the calcium aluminate of the cement according to the invention.
Indeed, the quantity and the nature of the crystalline mineralogical phases present in the cement according to the invention account for the chemical composition of said calcium aluminate.
In the remainder of the description, these "crystallized mineralogical phases" will sometimes be called "mineralogical phases".
Here in particular, the crystalline mineralogical phases describe both the atomic scale structure and the chemical composition of calcium aluminate, in that they involve several different compounds.
In particular, here, the mineralogical phases of the calcium aluminate of the cement according to the invention involve lime C, alumina A and silica S.
In general, the crystalline mineralogical phases of calcium aluminates are numerous. Among them, there are: phases comprising only lime C and alumina A, such as: the phase of monocalcium aluminate CaAl 2 O 4 noted CA, the crystalline mesh of which comprises a lime molecule C for a alumina A molecule, - CaAl407 calcium bialuminate phase denoted CA2, whose crystalline mesh comprises a molecule of lime C for two molecules of alumina A, - the phase of calcium hexaaluminate CA6 noted, whose crystalline mesh comprises a molecule of lime C for six molecules of alumina A, - the phase of tricalcium aluminate denoted C3A, whose crystal lattice comprises three lime molecules C for a molecule of alumina A, - the phase of hepta dodecacalcium aluminate denoted C12A7, the crystalline mesh of which comprises two lime molecules C for seven molecules of alumina A; Phases comprising only lime C and silica S, such as: the monocalcic silicate phase denoted CS, whose crystalline mesh comprises a lime molecule C for a silica S molecule; the dicalcium silicate phase denoted by C2S, the crystalline cell of which contains two lime molecules C for a silica S molecule; the tricalcium silicate phase, denoted C3S, whose crystalline mesh comprises three lime molecules C for a silica molecule S; the tricalcium bisilicate phase, denoted C3S2, whose crystalline mesh comprises three lime molecules C for two molecules of silica S; Phases comprising only alumina A and silica S, such as: the tri-aluminate bisilicate phase denoted A3S2, whose crystalline mesh comprises three molecules of alumina A for two molecules of silica S; Phases comprising both lime C, alumina A and silica S, such as: the phase of dicalcium aluminate silicate denoted C2AS, the crystalline mesh of which comprises two molecules of lime C for a Alumina molecule A and a silica molecule S, - the monocalcium alumina bisilicate phase denoted CAS2, the crystalline mesh of which comprises a molecule of lime C for one molecule of alumina A and two molecules of silica S; this list is not exhaustive.
These mineralogical phases are generally chosen according to the properties that they provide to the calcium aluminate cement, especially in terms of the reactivity and mechanical property of the cured final material.
It is common to graphically represent in a ternary diagram the different mineralogical phases that a calcium aluminate can adopt as a function of the relative proportion of each of the three lime compounds C, alumina A and silica S in said calcium aluminate.
Such a ternary diagram is represented in FIG. 1, showing some of the different mineralogical phases that can coexist in a calcium aluminate, as a function of the mass proportion of lime C, alumina A and silica S contained in said calcium aluminate.
In this diagram, we can read the mass fraction of lime C contained in the calcium aluminate on the side of the triangle situated between the vertices A and C, the mass fraction denoting the mass of lime C contained in the calcium aluminate by relative to the total mass of lime C, alumina A and silica S contained in said calcium aluminate.
This mass fraction of lime C is found inside the ternary diagram all along a line parallel to the side of the triangle opposite to the C summit.
Similarly, we can read the mass fraction of alumina A contained in calcium aluminate on the side of the triangle between the S and A vertices, and this mass fraction of alumina A is found inside the ternary diagram while along the line parallel to the side of the triangle opposite the vertex A.
Likewise, the mass fraction of silica S contained in the calcium aluminate on the side of the triangle situated between the vertices C and S, and this mass fraction of silica S is found inside the ternary diagram all along the right parallel to the side of the triangle opposite the S-vertex
In addition, on this ternary diagram, appear particular points which represent pure mineralogical phases. In other words, if the composition of the crystalline part of the calcium aluminate corresponds exactly to the molar fraction of lime C, alumina A and silica S of this particular point, then said crystalline part of the calcium aluminate comprises 100% of this particular crystallized mineral phase. This is the case for example at the C2AS point, or CA point or points CA2 or CA6.
In practice, it is rare for calcium aluminate to comprise a single pure phase, it more generally comprises several phases that coexist.
Here, in the calcium aluminate according to the invention, the majority crystallized mineralogical phases are the following: the CA2 phase, called the first crystallized mineralogical phase, the C2AS phase, called the second crystallized mineralogical phase.
More particularly, remarkably, the mass fraction of all of said first and second mineralogical phases CA2, C2AS in said calcium aluminate is greater than or equal to 80%.
In other words, the cumulative mass of the first and second mineralogical phases CA2, C2AS represents at least 80% of the total mass of calcium aluminate calcium aluminate cement according to the invention.
Thus, unlike the calcium aluminates described in the state of the art, whose majority mineralogical phase is the CA phase, here, the majority mineralogical phase or phases are the first and second CA2, C2AS mineralogical phases.
The remaining 20% of the calcium aluminate of the cement according to the invention, in mass relative to the total mass of said calcium aluminate, can comprise minority mineralogical phases such as: the phase CA, called third crystallized mineralogical phase, and the CA6 phase, called the fourth crystallized mineralogical phase.
Indeed, as shown in the ternary diagram of Figures 1 and 2, these third and fourth CA, CA6 mineralogical phases are in close proximity to the first and second mineralogical phases CA2, C2AS, so that during the manufacture of the Calcium aluminate of the cement according to the invention, it is very likely to form these third and fourth CA, CA6 mineralogical phases.
Preferably, the mass fraction of all the third and fourth crystalline mineralogical phases CA, CA6 in said calcium aluminate calcium aluminate cement according to the invention is less than or equal to 20%.
The remaining 20% of the calcium aluminate of the cement according to the invention may also comprise the minority compounds constituting the impurities of the calcium aluminate according to the invention mentioned above: iron oxide Fe 2 O 3, titanium oxide TiO 2, oxide S03 sulfur, magnesium oxide MgO, or alkaline compounds.
This remaining 20% also comprises the amorphous part of the calcium aluminate of the cement according to the invention, if one exists.
On the ternary diagram of Figures 1 and 2, there is a particular line D connecting the particular points representing the first and second mineralogical phases CA2, C2AS.
If the calcium aluminate of the cement according to the invention belongs to this particular straight line D, then it comprises between 100% of the first CA2 mineralogical phase and 100% of the second C2AS mineralogical phase.
In other words, if the calcium aluminate of the cement according to the invention belongs to this particular line D, this calcium aluminate is crystalline, and the mass fraction of all of said first and second mineralogical phases CA2, C2AS in the aluminate of calcium of the cement according to the invention is equal to 100%.
Thus, for the mass fraction of all of said first and second mineralogical phases CA2, C2AS in said calcium aluminate to be greater than or equal to 80%, this calcium aluminate must be located in a zone Z close to this particular line D .
This zone Z is represented graphically in FIGS. 1 and 2. The points v, w, x and y of the figures correspond to the following mineralogical compositions: the point v comprises 80% of the first CA2 mineralogical phase and 20% of the fourth CA6 mineralogical phase the point w comprises 80% of the first CA2 mineralogical phase and 20% of the third CA mineralogical phase; the x-point comprises 80% second C2AS mineralogical phase and 20% third CA mineralogical phase, and the y dot comprises 80 % of the first C2AS mineralogical phase and 20% of the fourth CA6 mineralogical phase.
Thus, the area of the ternary diagram delimited by the contour connecting the points [v - CA2 - w - x - C2AS - y - v] corresponds to the zone Z within which the sum of the first and second phases CA2, C2AS is greater than or equal to 80%.
In addition, it is possible to find the chemical composition of a calcium aluminate knowing its position in the ternary diagram.
For example, the composition of the point Y of the ternary diagram of FIGS. 1 and 2 is 34.4% of lime C, 48.1% of alumina A, and 17.5% of silica S.
Thus, according to the same principle, the ranges of chemical composition in lime C, alumina A and silica S of any calcium aluminate belonging to zone Z can also be determined graphically on the ternary diagram by means of Figure 2.
Moreover, surprisingly, the first and second mineralogical phases CA2, C2AS have a particular reactivity when they are in the presence of water.
Indeed, these first and second CA2, C2AS mineralogical phases are not very reactive with water at room temperature. In other words, they are adapted to react very slowly with water at room temperature.
Here it is meant that a mineralogical phase reacts with water when hydrated by water, and it is possible to characterize this reactivity by a quantity called the "degree of hydration" of the mineralogical phase.
The degree of hydration reflects the ability of a mineralogical phase to be hydrated by water, that is to say that the molecules constituting the crystal lattice of said mineralogical phase pass into solution in water form. ion, ie it is to evaluate the ability of the bonds existing between the molecules constituting the mineralogical phase to be broken by interaction with water. Nevertheless, as will be demonstrated in the examples, the first and second mineralogical phases CA2, C2AS are adapted to react effectively with water under the effect of a rise in temperature.
In other words, the degree of hydration of these first and second mineralogical phases increases with temperature.
In particular, these first and second mineralogical phases CA2, C2AS are adapted to react with water much faster than at ambient temperature when the outside temperature is between 50 degrees Celsius (° C) and 300.degree. preferably between 80 ° C and 280 ° C.
Advantageously, it is also possible to adjust the relative amount of each of the first and second mineralogical phases CA2, C2AS included in the calcium aluminate cement according to the invention to adjust the reactivity of the calcium aluminate cement according to the invention. at this temperature, from the degree of hydration of the first and second crystalline mineralogical phases CA2, C2AS at a given temperature. Unlike the first and second CA2, C2AS mineralogical phases, the third CA mineralogical phase is known to be very reactive at ambient temperature when it is in the presence of water, which is why its mass fraction in aluminum aluminate Calcium cement according to the invention is maintained less than or equal to 20% so as to maintain the characteristics of long workability of the cement according to the invention.
The fourth CA6 mineralogical phase is, in turn, completely inert regardless of the temperature to which it is subjected, ambient or high. Thus, it does not hydrate even during a rise in temperature.
On the other hand, when it is present in calcium aluminate, it contributes significantly to the high cost of producing said calcium aluminate because it contains a lot of alumina, which is the most expensive part of said calcium aluminate. This is why its mass fraction in the calcium aluminate of the cement according to the invention is kept less than or equal to 20%.
Thus, very advantageously, the cement according to the invention comprising few of these third and fourth phases CA, CA6 reacts slowly when it is mixed with water at ambient temperature, without the need to add a retarder, and it is advantageous from an economic point of view.
For example, a particularly useful calcium aluminate cement according to the invention comprises, by weight relative to the total mass of said calcium aluminate: - 50% to 60% of the first crystallized mineral phase CA2; - 26% to 32% second crystallized mineral phase C2AS; - 2.5% to 3.5% of the third CA crystallized mineralogical phase; - 0.5% to 1.5% of a fifth crystallized mineralogical phase of C4AF tetracalcium ferroaluminate; -10% to 15% additional crystalline mineralogical phases.
Thus, this composition according to the invention has both a majority of first and second crystalline mineralogical phases CA2, C2AS and a minority of crystalline mineralogical phases CA, CA6.
More specifically, a calcium aluminate cement according to the invention that can be envisaged comprises exactly, by weight relative to the total mass of said calcium aluminate: 55% of first crystallized mineral phase CA2; - 29% second crystallized mineral phase C2AS; - 3% of third crystallographic mineralogical phase CA; - 1% of a fifth crystallized mineralogical phase of C4AF tetracalcium ferroaluminate; - 12% more crystalline mineralogical phases.
In the diagram of FIG. 2, this particular composition is found in point I. It is very close to the particular line D and even appears to belong to this particular line D in FIG.
Furthermore, to manufacture the calcium aluminate cement according to the invention, an operator co-grinds, that is to say mix and grind in a single operation, bauxite and limestone to obtain a powder comprising particles whose maximum diameter is less than or equal to 100 microns (μm). The co-grinding operation may be carried out using a ball mill or any other grinder known to those skilled in the art.
The powder obtained at the end of this co-grinding operation is then granulated with water, that is to say that the fine powder particles are agglomerated with water to form granules with a diameter larger than that of the powder.
These granules are then introduced into an alumina crucible which is itself introduced into an electric furnace. The electric furnace containing the crucible is heated to a temperature of 1400 ° C. in a temperature range of 600 ° C. per hour. When the electric oven has reached 1400 ° C, a 6-hour cooking stage is applied.
At the outlet of the electric furnace, the calcium aluminate granules are finely ground so as to form the powder forming the calcium aluminate cement according to the invention.
Advantageously, the calcium aluminate cement powder according to the invention has a Blaine specific surface area measured according to the NF-EN-196-6 standard, of between 2200 square centimeters per gram and 4500 square centimeters per gram.
Preferably, the Blaine specific surface area of the calcium aluminate cement according to the invention is between 2900 and 3900 square centimeters per gram.
The higher the Blaine surface area, the finer the grains constituting the powder.
In addition, advantageously, the cement according to the invention having such a Blaine specific surface is suitable when it is mixed with water, to have an optimal contact surface with this water.
In addition, the cement according to the invention having this Blaine specific surface is adapted to be mixed homogeneously with a large quantity of water, that is to say that the cement is adapted to be dispersed in a large quantity of water. water equivalently at any point in the mixture.
In other words, even in the presence of a large amount of water, the cement according to the invention does not come out.
The calcium aluminate cement according to the invention can be mixed with water to form a cementitious composition.
More specifically, the cementitious composition according to the invention may comprise compounds other than the calcium aluminate cement according to the invention, such as: cementitious additions chosen from: fly ash and / or high granulated slag and / or a silica flour and / or silica fume and / or metakaolin, - aggregates of greater or lesser diameters selected from: quartz and / or fine limestone and / or sand, and additives of any kind known to those skilled in the art, for example fluidifiers or setting retarders.
Whatever the compounds included in the cementitious composition, the calcium aluminate cement present reacts with the water, that is to say that a chemical reaction, commonly called "hydration", occurs between the Calcium aluminate cement and water, during which the molecules constituting the crystalline and / or amorphous parts of the cement according to the invention are hydrated by water, namely that they pass into solution in water in the form of ions.
Conventionally, because of this chemical reaction, the consistency of the cementitious composition formed by the mixture between water and cement according to the invention is likely to change over time.
More precisely, three phases of evolution of said cementitious composition can be identified, these three phases constituting the "global hardening" of the cementitious composition: a first phase, called the thickening phase, during which the viscosity of the cementitious composition cementitious composition increases slowly, without preventing its implementation; a second phase, called the setting phase or the hydraulic setting phase, during which the cementitious composition hardens rapidly; and a third phase, called the final hardening phase, during which the cementitious composition continues to harden more slowly.
The duration of the thickening phase can vary from one cement to another since it depends a lot on the reactivity of the cement used. The open time corresponds globally to the duration of this thickening phase. It is of the order of a few hours in general.
The duration of the thickening phase also depends on external parameters such as pressure, temperature, and the relative proportion between water and cement.
During the hydraulic setting phase, the cementitious composition rapidly changes from a liquid state to a solid state, these states being defined in the mechanical sense of the term, namely that the liquid state is a state in which the cementitious composition is deformed by irreversibly when it is subjected to a deformation, while the solid state is a state in which the cementitious composition can deform elastically when subjected to deformation.
In practice, it is considered that the cementitious composition has reached its solid state when, subjected to the Vicat test according to the ASTM C91 standard described later in the example portion, the Vicat needle is unable to pass entirely through the cementitious composition. On the contrary, it is considered that the cementitious composition is in its liquid state when, subjected to this same Vicat test, the Vicat needle passes entirely through the cementitious composition.
Thus, at the end of the hydraulic setting phase, the cementitious composition already has a cured appearance, so that it can be considered as a final hardened material. However, it continues to harden during the final hardening phase.
In practice, here, the invention proposes a use of the calcium aluminate cement according to the invention, according to which a) a cementitious composition is produced by mixing said calcium aluminate cement with water, b) sets up said cementitious composition, c) said cementitious composition is heated at a temperature between 50 ° C and 300 ° C, preferably between 80 ° C and 28 ° C, so as to promote the setting of the cementitious composition. In step a), a user forms the cementitious composition by mixing the calcium aluminate cement with all said other compounds optionally included in the cementitious composition, and with the water.
Initially, that is to say at the moment when water, cement and possibly said other compounds are mixed, the consistency of the cementitious composition formed is more or less fluid depending on the body of water it contains relative to the total mass of said cementitious composition.
The amount of water added to the cement according to the invention and to said possible other compounds depends mainly on the application for which the cementitious composition is intended.
For example, a user may choose to form a cementitious composition in the form of a fairly fluid paste.
According to a particular use of calcium aluminate cement according to the invention, in step a), the user can form an aqueous suspension of cement.
More specifically, in the case where the cementitious composition is an aqueous suspension exclusively formed by water and the cement according to the invention, the mass fraction of water in said aqueous suspension is between 15% and 45%.
The mass fraction of the water in this aqueous suspension, between 15% and 45%, amounts to a water / cement ratio of between 20% and 70%, said ratio being the ratio between the mass of water and the mass of water. dry cement forming the aqueous suspension.
These general considerations are known to those skilled in the art and the proportion of water to be added to the cement and any other compounds for each application will not be detailed further below. In step b), as long as the cementitious composition is in the thickening phase, the user can set up the cementitious composition.
For example, if the cementitious composition is in the form of an aqueous suspension, the user can pour the cementitious composition into a slot.
In particular, according to the particular use of the calcium aluminate cement according to the invention in the form of an aqueous suspension, in step b), the said aqueous suspension is injected into a petroleum well.
This injection is by means of one or more pumps that push the aqueous suspension in a tubular body to the bottom of the wellbore. Once at the bottom of the wellbore, this suspension can naturally rise to the surface, between the rock wall and the tubular body.
When the cementitious composition is in the form of a paste, the user can shape it to prefabricate objects of beam or slab type. In step c), the initiation of the hydraulic setting phase of the cementitious composition is promoted by heating the cementitious composition at a temperature of between 50 ° C. and 300 ° C., preferably between 80 ° C. and 280 ° C. .
More precisely, this heating of the cementitious composition can be voluntary or undergone.
Thus, in practice, according to the particular use of the cementitious composition in the form of an aqueous suspension for oil drilling wells, this aqueous suspension of cement is naturally heated between 50 ° C and 300 ° C by the surrounding rock, after its recovery the surface.
For example, at a depth between 3000m and 5000m below the surface, the temperature is generally between 120 ° C and 180 ° C, and the heating of the cementitious composition is then undergone.
Thus, advantageously, according to the particular use of the calcium aluminate cement according to the invention, the aqueous suspension has a satisfactory workability at ambient temperature, that is to say that its viscosity at room temperature is sufficiently low to allow its injection by means of pumps, and the curing of said aqueous suspension occurs after its injection into the well, when the surrounding temperature rises.
Advantageously, there is no need to add a retarder to the aqueous suspension thus formed. The user can also choose to activate the phenomenon of hydraulic setting of the cementitious composition according to the invention by heating said cementitious composition to a temperature chosen between 50 ° C and 300 ° C. It is then a voluntary heating.
Advantageously, the user can thus choose the moment at which the hydraulic setting phase is triggered, by choosing the moment at which he heats the cementitious composition.
Whether the heating is voluntary or undergone, the thickening phase corresponding globally to the open time is completed at the time of heating.
Examples
In the following part, examples have been implemented to evaluate the properties of calcium aluminate cement according to the invention, and compare them with those of other existing cements.
To do this, different cementitious compositions were formed from different calcium aluminate cements, including the cement according to the invention, and these cementitious compositions were characterized using several tests.
Two main aspects make it possible to characterize a cementitious composition: its workability which reflects the open time during which the cementitious composition has a viscosity adapted to its use, and its kinetics of hardening.
The kinetics of hardening reflect both the rate of thickening of the cementitious composition, the instant from which its hydraulic setting is initiated, and the mechanical strength achieved by the cured final material obtained from the cementitious composition after that It has totally reacted.
Of course, depending on the intended uses for the cementitious compositions, the workability and hardening kinetics sought may vary. 1 / Cements compared
In practice, here, a first, a second, and a third calcium aluminate cement (Cimentl, Ciment2, Ciment3) have been used to form different cementitious compositions whose properties have been compared.
More specifically, the first and second cements (Cimentl, Ciment2) are calcium aluminate cements of the prior art known under the trade names of Cement Milled® and SECAR®71.
The third cement (Ciment3) is a calcium aluminate cement according to the invention.
It is obtained according to the process described above, by co-grinding 63.5% of Bauxite and 36.5% of Limestone, by mass relative to the total mass of co-milled materials.
The table "Composition" below presents the chemical composition of this cement according to the invention Cement3, as well as the chemical composition of the raw materials used to obtain it (Bauxite and Limestone). These compositions are given in percentage by mass (%), that is to say that they indicate the mass of compound relative to the total dry mass of cement or raw material used.
Composition Table
The LOI line, namely Loss on generation, or Loss on Fire, includes here volatile elements such as residual moisture in the case of bauxite or carbon dioxide CO2 in the case of limestone.
Table 1 below gives the mineralogical phases contained in these first, second and third cements (Cimentl, Ciment2, Ciment3).
Table 1:
The notation na means that the cement does not include the corresponding mineralogical phase.
The mineralogical phase Ferrites essentially comprises the mineralogical phase of C4AF tetra-calcium iron-aluminate, hereinafter referred to as the sixth crystalline mineralogical phase. The crystalline mesh of this sixth crystallized mineralogical phase comprises four lime molecules C for a molecule of alumina A and an iron oxide Fe2O3, abbreviated by the letter F.
The "other" column includes the impurities included in these cements, namely at least one of the following compounds: iron oxide Fe 2 O 3, titanium oxide TiO 2. sulfur oxides SOs. maize oxides MaO. and comoose
alkali.
A fourth cement (Ciment4) was also used in comparison with the three calcium aluminate cements Cimentl, Ciment2, Ciment3.
This fourth Cement4 cement is a class G Portland cement conventionally known to those skilled in the art and often used in oil drilling type applications. 2 / thickening time
A first test to characterize the cements studied consisted in measuring the thickening time of different cementitious compositions obtained by mixing these cements with water.
The thickening time is a datum making it possible to assess the workability of the cementitious composition, in particular when it is in the form of an aqueous suspension.
As used herein, the thickening time is an estimate of the time after which the cementitious composition can no longer be pumped. In other words, it is the time after which an aqueous suspension is too viscous to be moved by means of a pump.
More specifically, the thickening time corresponds to the time elapsed between the moment when the water and the cement have been mixed to form the cementitious composition in the form of an aqueous suspension, and the moment when the consistency, so-called consistency Bearden (Bc), the cementitious composition has reached such a value that this cementitious composition can no longer be pumped, the consistency Bearden being expressed by means of a unitless quantity.
Here, the measurement of the thickening time is done according to ISO 14026-1, clause 10.3, and the thickening time is such that the cementitious composition has reached a Bearden consistency of 100 Bc, at 23 ° C., under pressure Atmosphere of 1 atmosphere (atm).
In practice, the measurement of this thickening time is carried out for example by means of a stirring blade adapted to rotate in the cementitious composition while measuring a torque. This measured torque makes it possible to appreciate the force that the blade must exert on the cementitious composition in order to be able to rotate. This pair is thus connected to the Bearden consistency of the cementitious composition.
Table 2 below shows different cementitious compositions which were formed from the three cimentl calcium aluminate cements,
Cement2, Cement3, and Portland cement Cement4, as well as the associated thickening time, at room temperature (23 ° C).
In this Table 2, the water / cement ratio represents the mass of water that has been introduced to form the cementitious composition, relative to the dry cement mass.
Table 2:
In Table 2, it can be seen that the Compol and Compo2 cementitious compositions formed from the calcium aluminate cements of the prior art Cimentl and Ciment2 exhibit relatively short thickening times (less than 2 hours) at room temperature. (23 ° C). If the user needs a time greater than these times of thickening in order to be able to use the cementitious compositions comprising the two cements Cimentl and Ciment2, he will have to add them retarders of setting.
The Compo4 cementitious composition comprising Cement4 confirms that the Portland cements have an average thickening time (around 5 hours) at room temperature (23 ° C.). This is why these cements are often used in applications requiring a long implementation time.
Compo3 cementitious composition comprising the calcium aluminate cement according to the invention Cement3 has a thickening time greater than 10 hours, which offers the possibility to the user to use - for example to transport, to pour, to inject, pump, etc. - Compo3 cement composition for a long time, without having to add retarder.
In addition, it has a thickening time almost twice that of the Compo4 cementitious composition at room temperature (23 ° C), even though it comprises less water and should therefore be more reactive to the comoosition Comoo4 cement.
The cement according to the invention Ciment3 therefore has a very high workability without addition of set retarder. Thus, it is particularly suitable for applications requiring a very long open time, and this without chemical pollution associated with the use of retarders. 3 / Viscosity
A second test to characterize the cements studied consisted in measuring the viscosity of certain cementitious compositions.
The viscosity makes it possible to appreciate the kinetics of hardening and the workability of these cementitious compositions.
This is to measure the rheology of the cement compositions, that is to say their ability to flow and / or to deform.
As used herein, the measurement of viscosity is in accordance with ISO 14026-2 clause 12.
More specifically, the implementation of the viscosity test is as follows: the cement is mixed with the chosen amount of water to form the cementitious composition, then this cementitious composition is placed on a rotary viscometer brand FANN® 35.
The rheology of the cementitious composition is then tested directly after the mixing between the cement and the water (initial Viscosity V1), or after a rest period of 10 minutes (Viscosity V2), at a temperature of 23 ° C., of 50 ° C. ° C or 80 ° C and at atmospheric pressure of 1 arnosphère (atm), for a speed of rotation of the viscometer of 3 revolutions per minute (rpm).
Table 3 below shows the various cementitious compositions tested and their respective viscosities V1 and V2 at 23 ° C., Table 4 shows similar cementitious compositions and their viscosity at 50 ° C., and Table 5 shows the same cementitious compositions as those of Table 4 and their viscosities at 80 ° C.
In these three tables 3, 4 and 5, the cement compositions tested depend both on the cement used, the Blaine specific surface chosen for the cement, and the chosen water / cement ratio.
Table 3
Thus, the Compo5 cementitious composition comprising the calcium aluminate cement of the prior art Ciment2 has an initial viscosity V1 acceptable to be handled, but its viscosity after 10 minutes is that of a gelled cementitious composition. Therefore, as soon as the Compo5 cementitious composition is left immobile for too long, it can no longer be handled. This is particularly troublesome when it is desired to move such a cementitious composition by means of pumps, which could then be damaged as soon as they stop.
On the other hand, the cementitious compositions according to the CompoO Compo6 invention are particularly advantageous insofar as their initial V1 viscosities are low (less than 20), which facilitates their transport by means of a pump. Their viscosity V2 after a pause also remains low enough for them to be pumped.
Thus, the kinetics of hardening of the cementitious compositions comprising the calcium aluminate cement according to the invention Cement3 is much slower than those of the cementing compositions of the prior art, which is an advantage for uses requiring a long handling.
In addition, Table 3 also gives an indication of the reactivity of the Ciment3 calcium aluminate cement according to the invention as a function of the Blaine surface area. It is noted that the higher the Blaine specific surface area, the higher the initial viscosity and the viscosity after pause. So, the kinetics of hardening accelerates when the Blaine specific surface
increases, reflecting the fact that the finest powder grains are more easily hydrated by water because they have a larger reactive surface.
Table 4
Comparing Tables 3 and 4, it can be seen that the initial viscosity of the Compo11 cementitious composition of Table 4 comprising the calcium aluminate cement of the prior art Ciment2 increases as the temperature increases, even though it comprises more than water than the similar cementitious composition Compo5 of Table 3.
In addition, as in the case of the Compo5 cementitious composition, the V2 viscosity after a break in the Compol 1 cementitious composition is also too great for this Compol 1 cementitious composition to be used in pumps without adding a retarding agent.
In addition, the cementitious compositions according to the invention Compol 2 to Compol 4 have low initial viscosities V1 and viscosities V2 after a pause time, which still allows their use as well as their transport by means of pumps.
In addition, at this temperature (50 ° C.), the Blaine specific surface plays an important role on the viscosity: the higher the Blaine specific surface area, the higher the viscosity increases.
Table 5
Table 5 shows that at 80 ° C., the Compo11 cimetary composition comprising the calcium aluminate cement of the prior art Ciment2 can not be used because its viscosity is too high when mixed with water.
The initial viscosity V1 of the cementitious compositions comprising the cement according to the invention Ciment3 at 80 ° C. is of the same order of magnitude as at 50 ° C.
On the other hand, the rise in temperature influences the viscosity V2 after a pause time of the Compo12 to Compo14 cementitious compositions. In fact, the viscosity after pause increases sharply between 50 ° C. and 80 ° C., and even more so if the Blaine specific surface is large. This confirms the fact that the temperature promotes the reaction between water and cement according to the invention Cement3. 4 / Mechanical resistance On the other hand, it is also possible to appreciate the kinetics of hardening of the cementitious compositions by measuring the mechanical strength achieved by the cured final material obtained after reaction between water and cement.
In practice, the cementitious composition is formed by mixing the water and the cement, and then the cementitious composition is left to rest for 24 hours, at a chosen temperature and a chosen pressure, before measuring the mechanical strength according to the ISO 14026-1 standard. clause 9.2.
Table 6 shows the mechanical strengths of the three Compol, Compo2 and Compo3 cementitious compositions after 24 hours at 37 ° C and under atmospheric pressure (R1), after 24 hours at 60 ° C and under atmospheric pressure (R2), and after 24 hours at 110 ° C and under pressure of 20.7 MegaPascal (R3).
The mechanical resistances R1, R2 and R3 are given in MegaPascal (MPa).
Table 6
As early as 37 ° C., the mechanical strength developed by the Compol and Compo2 cementitious compositions comprising the calcium aluminate cements according to the prior art Cimentl and Ciment2 is important, which confirms the fact that these Compol and Compo2 cementitious compositions react at low levels. temperature.
On the contrary, the Cement3 cementitious composition comprising the cement according to the invention Cement3 has a mechanical strength of zero at 37 ° C., and almost zero at 60 ° C., which indicates that this cement is only very slightly reactive below 60 ° C. C. Thus, it reinforces the fact that the reaction of the cement according to the invention with water is naturally retarded at temperatures below 60 ° C, without the need to add retarder thereto.
After 24 hours at 110 ° C., the mechanical strengths of the Compol and Compo2 cementitious compositions are higher, which proves that these cementitious compositions react more rapidly at this temperature than at a temperature of 37.degree. At 110 ° C., the Compo3 cementitious composition also develops a mechanical strength of the order of about twenty megaPascals. Thus, the reaction between the cement according to the invention and the water is favored by high temperatures.
Therefore, the calcium aluminate cement according to the invention has a temperature-controlled curing kinetics without the need to add retarder.
In addition, at 110 ° C, the mechanical strength R3 developed by the cementitious Compo3 composition comprising the calcium aluminate cement according to the invention Cement3 is similar to that of calcium aluminate cements usually used and known to date ( of the order of 20 MPa). 5 / Setting time and contamination
Another test focused on the effect of contamination of a Portland cement
by a cement according to the invention. For this purpose, the setting time of different cementitious compositions comprising both a Portland cement and a calcium aluminate cement has been measured.
As used herein, setting time is measured according to ASTM C91 using a Vicat needle.
The Vicat test consists of mixing the water and the cement to form the cementitious composition, then to drop a Vicat needle into the cementitious composition, which is static, at regular intervals of time. As long as the needle sinks to the bottom of the cementitious composition, it is considered that the setting time is not reached, as soon as it sinks without being able to go to the bottom of the cementitious composition, has reached the setting time.
In practice, the setting time thus corresponds to the time which elapsed between the moment when the cement and the water were mixed to form the cementitious composition in a liquid state, and the moment when the cementitious composition is passed through a state strong enough that the Vicat needle can not pass through it completely but only partially, at a temperature of 23 ° C and under atmospheric pressure (1atm).
Table 7 below shows the setting times, in minutes, of different cementitious compositions comprising a certain proportion of calcium aluminate cement mixed with a Portland cement. The Portland cement used is a class H Portland cement.
In Table 7, the percentages give the mass of calcium aluminate cement added relative to the total dry mass of cement used. Thus, the complement to reach 100% corresponds to the mass of Portland cement contained in the total dry mass of cement.
The ratio water / cement is 0.38, that is to say that the water used represents 38% of the total dry mass of cement used.
Table 7
Table 7 shows the effect on setting time of the contamination of a Portland cement by a calcium aluminate cement. From Table 7, prior art calcium aluminate cements Ciment1 and Ciment2 have a significant effect on the setting time of the Portland cement used. Indeed, while the only Portland cement, corresponding to the first column, has a relatively long setting time of 400 minutes, the setting time observed for a mixture with 15% of calcium aluminate cement Cement and Ciment2 is very short (10 and 20 minutes). This means that a cementitious composition containing a Portland cement and a calcium aluminate cement of the prior art reacts very rapidly, preventing the use of such a cementitious composition for applications requiring long implementations. Such cementitious compositions can not therefore be used in drilling well type applications for example.
On the other hand, the contamination of Portland cement with cement according to the invention Cement3 has little effect, at ambient temperature, on the setting time of the cementitious composition. In fact, the setting time of a cementitious composition comprising 15% Cement3 and 85% Portland cement corresponds to 75% of the setting time of a cementitious composition comprising 100% Portland cement.
Therefore, the use of calcium aluminate cement according to the invention Cement3 is facilitated compared to other calcium aluminate cements insofar as it is not necessary to clean the installations before these facilities can be used. for a Portland cement. 6 / Degree of hydration
A final test consisted of evaluating the influence of temperature on the hydration rate of the cement according to the invention Cement3.
This test is based on electron microscopic observations allowing quantification according to the Rietvled method as well as X-ray diffraction measurements.
In practice, a Compo15 cementitious composition was formed by mixing water with the cement according to the invention Cement3 in a water / cement ratio of 0.44, that is to say so that water represents 44% by weight. % by weight relative to the total dry mass of cement.
A Compo16 cementitious composition was also formed by mixing water with the cement of the prior art Ciment2 in a water / cement ratio of 0.44.
These Compo15 and Compo16 cementitious compositions were then subjected to an X-ray diffraction test as soon as they were formed (D1), after standing at 23 ° C. (D2) for 24 hours, after autoclaving. for 24 hours at 120 ° C (D3), and after autoclaving for 24 hours at 180 ° C (D4).
The results of this X-ray diffraction test make it possible to estimate the percentage of each mineralogical phase present in the Compo15 and Compo16 cementitious compositions as well as the remaining free water, in mass relative to the total mass of the Compol cementitious composition. , depending on the treatment they have undergone.
The results also make it possible to estimate the percentage of hydrates formed during the hydration reaction of water with Cement3 and Ciment2 cements, as a function of the different treatments undergone. Hydrates are compounds formed between water (denoted H) and hydrated chemical compounds from the mineralogical phases initially included in the cements studied.
In other words, the results of the X-ray diffraction test make it possible to estimate the degree of hydration of the mineralogical phases of the cement according to the invention Cement3 or of the cement of the prior art Ciment2, as a function of the temperature.
The term "free water" means water which is not engaged in bonds with ions from the different hydrated mineralogical phases, that is to say which does not already belong to a hydrate formed. In other words, it is the water still available to hydrate the existing mineralogical phases.
In Tables 8 and 9, the "other" phase groups together any impurities (Fe2O3 iron oxide, TiO2 titanium oxide, SO3 sulfur oxide, MgO magnesium oxide, and alkaline compounds).
Table 8 below presents the results of the X-ray diffraction test, namely the percentage of each mineralogical phase and of each hydrate present after each treatment undergone by the Compo15 cementitious composition.
Table 9 presents the results of the X-ray diffraction test, after each treatment undergone by the Compo16 cementitious composition.
Table 8
In this table 8, the "other" phase also includes the CA phase. This AC phase is present initially during the mixing between the cement3 and the water (column D1), and is absent from the mixture after 24 hours of reaction (columns D2, D3 and D4) because it has totally reacted with the water, which whatever the temperature.
As shown in Table 8, the first and second mineralogical phases CA2, C2AS react little, if any, below 120 ° C.
On the other hand, the first mineralogical phase CA2 reacts entirely from 120 ° C. In other words, from 120 ° C, the first CA2 mineralogical phase is fully hydrated with water.
The second C2AS mineral phase reacts from 120 ° C, but is less reactive than the first CA2 mineralogical phase.
Thus, the reactivity of the first CA2 mineralogical phase is favored by a temperature lower than that promoting the reactivity of the second C2AS mineralogical phase.
Table 9
Comparing Tables 8 and 9, it is noted that the hydrates C3AH6, AH3, and AH formed by the hydration reaction of the calcium aluminate cement of the prior art Ciment2 with water are also formed by the reaction of hydration of calcium aluminate cement according to the invention Cement3 with water.
In addition, during the hydration reaction of the calcium aluminate cement according to the invention Ciment3 with water, an additional hydrate C3AS (3-x) H4x is also formed.
Thus, the presence of the same hydrates in the cured final material obtained from the calcium aluminate cement of the prior art Ciment2 and in the final cured material obtained from the calcium aluminate cement according to the invention Cement3 shows that the chemical resistance properties of these cured end materials are similar.
Therefore, the cement according to the invention has chemical resistance properties similar to those already known calcium aluminate cements.
Thus, all of the experiments carried out show that the calcium aluminate cement according to the invention has slow curing kinetics at room temperature, which makes it possible to use it without setting retarder.
This kinetics of hardening can be adjusted according to the temperature and by choosing the relative proportion of first and second
CA2, C2AS mineralogical phase.
In addition, at room temperature, the calcium aluminate cement according to the invention has a low contaminating power on Portland cements.
Finally, the mechanical properties of the cured final material obtained from the calcium aluminate cement according to the invention are similar to those of the cured end materials obtained from the known calcium aluminate cements.

权利要求:
Claims (9)
[1" id="c-fr-0001]
A calcium aluminate cement comprising a calcium aluminate with a first crystallized mineral phase of CA 2 calcium bialuminate comprising a calcium oxide CaO for two aluminum oxides AI2O3 and / or a second crystallized mineral silicate phase of C2AS bicalcium alumina comprising two CaO calcium oxides for Al203 aluminum oxide and SiO2 silicon dioxide, characterized in that the mass fraction of all of said first and second mineralogical phases in said calcium aluminate is greater than or equal to 80%.
[2" id="c-fr-0002]
Calcium aluminate cement according to claim 1, wherein said calcium aluminate also comprises an amorphous portion, whose mass fraction in said calcium aluminate is less than or equal to 20%.
[3" id="c-fr-0003]
3. Calcium aluminate cement according to one of claims 1 and 2, wherein said calcium aluminate further comprises a third crystallized mineralogical phase of monocalcium aluminate CA comprising a calcium oxide CaO for an aluminum oxide Al203 and / or a fourth crystallized mineral phase of CA6 calcium hexaaluminate comprising a calcium oxide CaO for six Al203 aluminum oxides, the mass fraction of all of the third and fourth mineralogical phases in said calcium aluminate being less than or equal to 20%.
[4" id="c-fr-0004]
4. Calcium aluminate cement according to one of claims 1 to 3, comprising, by weight relative to the total mass of said calcium aluminate: - 0% to 5% of an iron oxide Fe 2 O 3, - 0 % to 5% of titanium oxide TiO 2, 0% to 5% of sulfur oxide SO 3, 0% to 5% of magnesium oxide MgO, 0% to 2% of alkaline compounds.
[5" id="c-fr-0005]
Calcium aluminate cement according to one of claims 1 to 4, in the form of a powder having a Blaine specific surface area measured according to the NF-EN-196-6 standard of between 2200 square centimeters per gram. and 4500 square centimeters per gram, preferably between 2900 and 3900 square centimeters per gram.
[6" id="c-fr-0006]
6. Ciment of calcium aluminates according to one of claims 1 to 5, comprising, by weight relative to the total mass of said calcium aluminate: - 50% to 60% of first crystallized mineralogical phase CA2, - 26% to 32% second crystallized phase C2AS, - 2.5% to 3.5% third crystallographic phase CA, - 0.5% to 1.5% of a fifth crystallized mineralogical phase of C4AF tetracalcium ferroaluminate, -10% to 15% additional crystalline mineralogical phases.
[7" id="c-fr-0007]
7. Cementitious composition comprising at least the calcium aluminate cement according to one of claims 1 to 6 mixed with water, and optionally cementitious additives such as fly ash and / or a granulated blast furnace slag and / or silica flour and / or silica fume and / or metakaolin, aggregates such as quartz and / or fine limestone and / or sand, and adjuvants.
[8" id="c-fr-0008]
8. Use of calcium aluminate cement according to one of claims 1 to 6, wherein: a) a cementitious composition is produced by mixing at least said calcium aluminate cement with water, b) one sets up said cementitious composition, c) said cementitious composition is heated at a temperature between 50 ° C and 300 ° C, preferably between 80 ° C and 20 ° C, so as to promote the setting of the cementitious composition.
[9" id="c-fr-0009]
9. Use of the calcium aluminate cement according to claim 8, wherein, in step a), the cementitious composition is in the form of an aqueous suspension, and according to which in step b), the Cement composition is placed in an oil well.

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CN112521113A|2020-12-04|2021-03-19|交通运输部公路科学研究所|Low-temperature hydration hardening gel material and preparation method and application thereof|

法律状态:
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2017-02-03| PLSC| Publication of the preliminary search report|Effective date: 20170203 |

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2017-05-19| PLFP| Fee payment|Year of fee payment: 3 |

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2021-07-26| PLFP| Fee payment|Year of fee payment: 7 |

优先权:

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申请号 | 申请日 | 专利标题

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FR1557167A|FR3039538B1|2015-07-27|2015-07-27|CALCIUM ALUMINATE CEMENT WITH LONG OUVABILITY AND HARDENING PROMOTED BY TEMPERATURE ELEVATION, AND USE THEREOF|FR1557167A| FR3039538B1|2015-07-27|2015-07-27|CALCIUM ALUMINATE CEMENT WITH LONG OUVABILITY AND HARDENING PROMOTED BY TEMPERATURE ELEVATION, AND USE THEREOF|

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US15/744,227| US10647613B2|2015-07-27|2016-07-27|Long-workability calcium aluminate cement with hardening promoted by a temperature increase, and related use|

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BR112018001711-6A| BR112018001711B1|2015-07-27|2016-07-27|CALCIUM ALUMINATE CEMENT, CEMENT COMPOSITION AND USE OF CALCIUM ALUMINATE CEMENT|

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EP16757304.7A| EP3328811B1|2015-07-27|2016-07-27|Long-workability calcium aluminate cement with hardening promoted by a temperature increase, and related use|

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JP2018503779A| JP6803370B2|2015-07-27|2016-07-27|Long-workability calcium aluminates cement with curability promoted by increasing temperature and its use|

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EA201890385A| EA036363B1|2015-07-27|2016-07-27|Long-workability calcium aluminate cement with hardening promoted by a temperature increase, cementitious composition comprising same and method of use thereof|

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CN201680044233.9A| CN107848887A|2015-07-27|2016-07-27|The long-term machinable aluminous cement and associated uses for promoting hardening are raised by temperature|

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KR1020187002635A| KR20180034445A|2015-07-27|2016-07-27|Long working calcium aluminate cements and related uses with curing properties promoted by temperature rise|

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DK16757304.7T| DK3328811T3|2015-07-27|2016-07-27|Calcium aluminate cement with long machinability and with tempering promoted by a rise in temperature and associated application|

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PCT/FR2016/051948| WO2017017376A1|2015-07-27|2016-07-27|Long-workability calcium aluminate cement with hardening promoted by a temperature increase, and related use|

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ES16757304T| ES2796359T3|2015-07-27|2016-07-27|Long workability and hardening calcium aluminate cement favored by a rise in temperature and associated use|

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ZA2018/00407A| ZA201800407B|2015-07-27|2018-01-19|Long-workability calcium aluminate cement with hardening promoted by a temperature increase, and related use|

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US16/872,228| US11208353B2|2015-07-27|2020-05-11|Long-workability calcium aluminate cement with hardening promoted by a temperature increase, and related use|

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HRP20200865TT| HRP20200865T1|2015-07-27|2020-06-01|Long-workability calcium aluminate cement with hardening promoted by a temperature increase, and related use|