Abstract:
Composition comprising water- and air-hardenable binders and its use notably to the preparation of a product having the aspect and the properties of a natural stone. 
     Composition comprising water- and air-hardenable binders, exhibiting after hardening properties comparable at least to those of a natural stone or of a concrete, characterised in that it includes, as binders:
       natural and air-borne hydraulic lime, and   moulding plaster.

Description:
BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention relates to a composition comprising water- and air-hardenable binders, exhibiting after hardening properties comparable at least to those of a natural stone or of a concrete. 
     The invention also concerns the use of the composition according to the invention to the realisation of moulded objects having the aspect and the properties of the stone, in particular of structures and of statutes, of slabs, paving blocks, city or interior furniture, chimneys and analogous objects. 
     The invention also concerns the application of the composition according to the invention to the realisation of a finish-polishing mortar or finishing and decoration coats. 
     2. Description of the Related Art 
     Among the hydraulic binders known, lime, plaster and cement can be mentioned, notably. 
     Lime, which has been known for a very long time, has been used in the past notably in the building trade, for example for sealing stones. 
     Lime has been far less used since the discovery of cement which enables to realise mortars, concretes and moulded objects having mechanical properties vastly greater than those which may be obtained with lime. 
     The objects and coats realised on the basis of cement have the major shortcoming of requiring long hardening times which slow down considerably the production rates. 
     On the other hand, the mortars and concretes obtained with cement are subject to retraction when hardening which promotes the formation of microcracks, thereby making moulded objects brittle. 
     Besides, when mortar or concrete is cast into a mould, the cast matter is generally not self-placing, so that it is necessary to use tools for kneading, vibrating or flattening the surface of the matter. 
     Plaster is used currently for moulding diverse objects. 
     However, plaster does not resist to the contact of water, so that the moulded objects made of plaster may not be used outdoors. 
     Moreover, the mechanical properties of plaster are vastly lower than those of concrete. 
     BRIEF SUMMARY OF THE INVENTION 
     The purpose of the present invention is to remedy the shortcomings above while offering a water- and air-hardenable composition exhibiting after hardening properties comparable at least to those of a natural stone or of a concrete without exhibiting the shortcomings of the former. 
     According to the invention, said composition is characterised in that it includes, as binders:
         natural and air-borne hydraulic lime, and   moulding plaster.       

    
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     By hydraulic lime is meant a mixture including Ca(OH) 2  essentially and low calcium silicate content. The air-borne lime is Ca(OH) 2 . These definitions exclude quick lime and dead lime. 
     It has been noticed surprisingly that the mixture of two binders (plaster and hydraulic lime) a priori incompatible, known and used separately for a very long time, enables to realise products having unexpected properties as regards those known for each of these binders. 
     The innovating advantages and aspects of the composition according to the invention are detailed below:
         the first advantage of that composition lies in that it enables to obtain a mineral material having the (internal and external) aspect of a copying stone,   the second corresponds to the fact that the physical characteristics of the material created are very close to the material to be imitated: hardness, absorption, density, porosity, resistance, etc . . . ,   the third corresponds to the use of a mixture of two binders: sulphatic binders (plaster) and lime (air-borne and natural hydraulic lime),   the fourth point, of technical order, enables to mould difficult and complex parts with very satisfying superficial aspect and to obtain high short-term resistances (resistance equivalent to that of a calcareous stone after 15 minutes at 3 hours),   the fifth point corresponds to the lack of retraction and therefore enables to minimise microcracking of the material relative to the desiccation thereof (a problem frequently encountered on the extent products).       

     Besides, another important aspect of the material obtained according to the invention lies in that it may be offered in different ranges of products enabling to obtain different features in fresh or hardened condition in relation to the material to be imitated or of the type of implementation (finish-polishing mortar, moulding material, self-placing material, absence of bubbling, aspect, veins . . . ), by simple modification of the different proportions of the different ingredients. 
     Preferably, the composition according to the invention includes moreover mineral loads, calcareous and/or siliceous loads, according to the desirable properties. 
     Preferably also the composition according to the invention includes additionally a fluidising and water-reducing adjuvant of the type used in current compositions in artificial materials (based on cement, plaster, etc . . . ). 
     For exemplification, this adjuvant may be the high water-reducing super-plasticizer CIMFLUID 2002 available from Axim (new generation adjuvant based on modified polycarboxylate): dosage of the order of 1 to 3% of the binder. 
     According to an advantageous version of the invention, the composition includes additionally at least one adjuvant selected among the group comprising a set retardant, an anti-bubbling agent, an air entrainer and the mixtures thereof. 
     In this view, both following adjuvants should be mentioned in particular: 
     Retardant (Retardant P from Lafarge Prestia): dosage to be suited relative to the external temperature and to the setting time desired (0% corresponds to approximately 10 to 15 min and 1% of the order of 1 hour setting delay), powder adjuvant, 
     Cimparement (An anti-bubbling agent based on synthetic polymer and alcohol ether): dosage of the order of 0.1 to 0.5%, liquid adjuvant. 
     According to the result requested, the proportion in weight of lime and that of plaster may range between 25 and 75% of the total weight of both these binders. 
     Besides, the quantity of mineral loads may range between 0.5 and 6 times the weight of both these binders. 
     On the other hand, the proportion in weight of the adjuvants may range between 0 and 5% of the binders. 
     There are two examples of formulation of the composition according to the invention: 
     
       
         
               
               
               
             
               
               
               
               
               
               
             
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                   
               
               
                   
                 Material 1: 
                 Material 2: 
               
               
                   
                 Fontvieille stone type 
                 Marble type 
               
               
                 Nature of the constituents 
                 tender calcareous stone 
                 harder stone 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 1. 
                 Hydraulic lime NHL 
                 315 
                 Kg/m 3   
                 500 
                 Kg/m 3   
               
               
                 2. 
                 Moulding plaster 
                 315 
                 Kg/m 3   
                 500 
                 Kg/m 3   
               
               
                 3. 
                 Fine calcareous load 
                 750 
                 Kg/m 3   
                 500 
                 Kg/m 3   
               
               
                   
                 (0/0.6 mm): mixture of 
               
               
                   
                 crushed powder marble 
               
             
          
           
               
                 4. 
                 Siliceous load 
                 450 
                 Kg/m 3   
                 — 
               
               
                   
                 (0/0.6 mm) 
               
               
                 5. 
                 Siliceous fine 
                  80 
                 Kg/m 3   
                 — 
               
             
          
           
               
                 6. 
                 New generation fluidiser 
                  18 
                 Kg/m 3   
                  20 
                 Kg/m 3   
               
               
                   
                 adjuvant 
               
               
                 7. 
                 Other adjuvants: 
                 1 to 5 
                 Kg/m 3   
                 1 to 5 
                 Kg/m 3   
               
               
                   
                 retardant, anti-bubbling 
               
               
                   
                 agent, air entrainer, etc . . . 
               
               
                 8. 
                 Water 
                 300 
                 Kg/m 3   
                 350 
                 Kg/m 3   
               
               
                   
               
             
          
         
       
     
     One of the advantages of the composition according to the invention lies in that it may be implemented in a relatively simple way with different types of material. Tests have been carried out with laboratory crushers, industrial kneading machines, concrete mixers and an electric drill-carried stirring system. The impact of the use of these different types of materials is carried forward to the kneading time. Indeed, the kneading energy is a major factor and enables the adjuvants to play their part as fluidisers. Thus, the smaller the kneading energy, the longer the kneading time should be in order to obtain a placing material. 
     Thus, the easiest kneading solution consists in injecting all the dry elements (or a pre-formulated mixture), then in introducing water gradually with the adjuvants. The material goes from a dry ground condition, through a wet condition, to a self-placing condition, finally. 
     The kneading time ranges generally between 1 and 10 minutes according to the matter and to the materials used. 
     According to the type of application (moulding, slab paving, finish-polishing mortar, etc . . . ) the rheology of the fresh material will be different (self-placing materials for moulding and, unctuous and sticky for finish-polishing mortars). 
     The hardening of the material (and hence the drawing if necessary) takes place between 15 minutes and 3 hours after the beginning of the kneading. This parameter may nevertheless be easily suited to the constraints. This item is a major point of the innovation. Indeed, it enables to increase the drawing rate in the field of prefabrication of concrete objects or parts, currently realised with cement. 
     No cure is necessary, since the material does not exhibit any self-desiccating retraction and the increase in resistances takes place essentially in open air by lime carbonation. 
     In order to put in evidence the characteristics of the materials obtained according to the invention and of the cement-based materials, different tests have been realised on these materials. The comparison of the results obtained with those indicated on the sheets produced and supplied by the carriers, is presented in the table below: 
     
       
         
               
               
               
               
             
           
               
                   
               
               
                   
                 Provence 
                 Formulation 
                   
               
               
                   
                 stone 
                 according to the 
                 Cement 
               
               
                   
                 (Estaillades) 
                 invention 
                 formulation 
               
               
                   
               
             
             
               
                 Apparent density 
                 1850 to 1950 
                 1850 
                   2100 
               
               
                 (Kg/m 3 ) 
               
               
                 Setting time 
                 N/A 
                 1 h 
                 6 to 12 h 
               
               
                 Porosity (%) 
                 27 to 31 
                  25 
                    19 
               
               
                 Capillarity 
                 70 
                  65 
                    29 
               
               
                 coefficient C 1   
               
               
                 (g/(m 2  · sec 0.5 )) 
               
               
                 Sound speed (m/s) 
                 2400 to 3200 
                 2610 
                   3500 
               
               
                 Compression 
                 10 to 25 
                  7 (after 2 hrs) 
                  4 (after 12 hs) 
               
               
                 mechanical 
                   
                 10 (after 3 days) 
                 25 (after 3 days) 
               
               
                 strength (MPa) 
                   
                 15 (after 28 days) 
                 40 (after 28 days) 
               
               
                   
                   
                 25 (after 90 days) 
                 40 (after 90 days) 
               
               
                   
                   
                 40 (long term) 
                 40 (long term) 
               
               
                 Flexion mechanical 
                 3 to 6 
                   8 
                     7 
               
               
                 resistance (MPa) 
               
               
                 Frost/defrost cycle 
                 40 
                  40 
                    35 
               
               
                 resistance (number 
               
               
                 of cycles) 
               
               
                 Surface hardness 
                 0.7 
                   0.6 
                     0.3 
               
               
                 at 28 days (mm) 
               
               
                 Retraction (μm/m) 
                 N/A 
                  50 
                  −700 
               
               
                 Swelling (μm/m) 
                 N/A 
                  200 
                    200 
               
               
                   
               
             
          
         
       
     
     The analysis of the results mentioned in the table below puts in evidence the main following indications:
         the density of the formulation according to the invention is approximately 15% smaller than that of the cement-based formulation and of the same order of magnitude as natural stone,   the general characteristics of the material according to the invention, are very close to those of Provence Stone-type calcareous stones,   the main advantages of the formulation according to the invention, comparatively to the cement formulation are: greater short-term resistance, the absence of retraction and smaller density. Besides, the long-term resistances and the hardness of both materials (formulation according to the invention and cement formulation) are of the same order of magnitude.       

     The tests have shown on the one hand that the formulation according to the invention might bring numerous advantages regarding the manufacturing process of materials having the aspect of calcareous stones (with respect to the cement-base formulations used currently). On the other hand, the cement-based formulation is naturally (binder type) difficult to optimise (see table thereafter). Indeed the characteristics of that formulation may not be improved without in-depth modification of the different components used. 
     
       
         
               
               
               
             
           
               
                   
               
               
                   
                 Cement-based 
                 Formulation according to the 
               
               
                 Characteristics 
                 formulation 
                 invention 
               
               
                   
               
             
             
               
                 Hardening time 
                 6 to 12 h 
                 2 to 3 h 
               
               
                 before 
                   
                 (optimisation of the utilisation 
               
               
                 drawing 
                   
                 of the tooling and of the 
               
               
                   
                   
                 working teams) 
               
               
                 Drawing 
                 3 MPa 
                 7 MPa (enables less risky 
               
               
                 resistance 
                   
                 and easier drawing) 
               
               
                 Long time 
                 30 to 40 MPa 
                 25 to 30 MPa 
               
               
                 resistance 
               
               
                 Workability 
                 Compulsory handover or 
                 Better workability, easier 
               
               
                   
                 vibration 
                 implementation 
               
               
                 Bubbling 
                 Important: Compulsory 
                 Vastly reduced: easy 
               
               
                   
                 handover or vibration 
                 implementation 
               
               
                 Others 
                 Compulsory handover or 
                 No handover (improved 
               
               
                   
                 vibration 
                 working conditions and result) 
               
               
                   
               
             
          
         
       
     
     Because of the characteristics mentioned above, the invention, may be used to the realisation of moulded objects having the aspect and the properties of the stone, in particular of structures and of statutes, of slabs, paving blocks, city or interior furniture, chimneys and analogous objects. 
     Similarly, the composition according to the invention may be used to the realisation of a repairing mortar by finish-polishing or a finishing decoration coat.