Patent Publication Number: US-4060425-A

Title: Super rapid hardening mixture

Description:
This invention relates to a super rapid hardening mixture which comprises a super rapid hardening cement and a bituminous emulsion, a rubber latex and/or a resin emulsion. In the prior art techniques, it is well known that a mixture of Portland cement and an asphalt emulsion can be used as a grout which has the elastic properties for a slab-type track structure. 
     The use of the mixture of portland cement and an asphalt emulsion is accompanied by the disadvantage that the mixture does not exhibit the desired strength for long period of time and hence the mixture can not be applied for a structure which has a restricted period of time for construction. 
     To eliminate of this defect, a mixture of a super rapid hardening cement containing calcium haloaluminate and an asphalt emulsion was made. However, this mixture did not provide a hardened mass of the higher strength in a short period of time (in from 1 to 3 hours) though the mixture hardened in a relatively short period of time. It was expected that a mixture could be prepared for which would relieve stress and which shows high strength in a short period of time. 
     The present study was initiated to attempt to formulate a mixture which would satisfy these demands and it has been found that a mixture of an asphalt emulsion and a super rapid hardening cement which comprises a clinker containing 11CaO.7Al 2  O 3  .CaX 2  (X is a halogen atom) mixed with anhydrite; one or more additives of a calcium aluminate material, a lime material, an amine, an ethylene glycol material and calcium sulphate hemihydrate, or a mixture thereof to which is added a set-controlling agent developed early high strength, and that further a mixture of a rubber emulsion and/or a resin emulsion in place of the above asphalt emulsion or two of the three emulsions and the above super rapid hardening cement also developed high early strength. 
     This invention relates to a super rapid hardening mixture which comprises a mixture of a super rapid hardening cement containing 11CaO.7Al 2  O 3 .CaX 2  (X is a halogen atom), 3CaO.SiO 2  and CaSO 4  as indespensable components, with one or more short range strength accelerators such as a calcium aluminate material, a lime material, an amine, an ethylene glycol material or calcium sulphate hemihydrate; a bituminous emulsion; and if necessary water, an aggregate, a filler and a foaming agent and/or a set controlling agent. In place of the bituminous emulsion, one or more mixtures selected from the group of a bituminous emulsion, a rubber latex and a resin emulsion can be mixed to form a super rapid hardening mixture. The super rapid hardening mixture will be stated simply as &#34;the mixture&#34; hereinafter. 
     In this invention, the super rapid hardening cement is prepared by adding anhydrite (CaSO 4 ) to the clinker powder containing from 1 to 60% by weight of 11CaO.7Al 2  O 3 .CaX 2  and more than 5% by weight of 3CaO.SiO 2 , in such amount that the weight ratio of Al 2  O 3  /SO 3  in the cement is from 0.4 to 3.0, or in addition to this cement, a set controlling agent is added. The set controlling agent is at least one member selected from the group consisting of a carboxylic acid such as gluconic acid, tartaric acid, citric acid 0r the like salts thereof, boric acid, the salts thereof such as borax, calcium borate and the like and a carbonate, sulfate or hydroxide of an alkali metal such as sodium, potassium or lithium. 
     The set controlling agent is used in a proportion of from about 0.02 to 8% by weight, preferably 0.05 to 5% by weight (inner parts) based on the weight of the super rapid hardening cement. (Unless otherwise indicated, all percentages shown are in weight percents and all parts and ratios and the like are by weight). 
     If the set controlling agent is added in an amount over or under the above range, the setting properties of the mixture can not be controlled. 
     Short range strength accelerators include, a calcium aluminate material such as CaO.Al 2  O 3 , 12CaO.7Al 2  O 3 , 3CaO.3Al 2  O 3  .CaF 2  and CaO.2Al 2  O 3 . The calcium aluminate material is used in an amount of 1 to 50%, preferably 5 to 40% by weight based on the weight of the mixture of the super rapid hardening cement and the calcium aluminate material. If the amount used is less than the lower limit, the effect is negligible. Over the upper limit, the handling time of the mixture of this invention becomes extremely short and difficult. 
     Suitable examples of a lime material include quick lime and slaked lime. The amount of the lime material used ranges from 0.1 to 25%, preferably from 0.5 to 15%, of the mixture. If the amount used is less than the lower limit, the effect of the addition is negligible. Over and over the upper limit, the setting properties of the mixture are uncontrollable. In case of the quick lime, because of the violent hydration reaction of quick lime, control of the handling time becomes difficult and the effect of the quick lime does not increase proportionally as the addition increase. 
     A properly calcined lime accelerates the hardening of the mixture by the heat of reaction without disturbing the fluidity of the mixture because it is gently hydrated. 
     It is desirable to use slaked lime from the viewpoint of the handling characteristics of the mixture. The lime materials can be more effective when they are used together with one of the calcium aluminate series materials described above. 
     Examples of the amine series materials are, monoethanolamine, diethanolamine, and triethanolamine. The amount of the amine series material employed ranges from 0.002 to 2.5%, preferably from 0.1 to 1%. When they are used together with calcium sulphate hemihydrate, the development of the short range strength of the mixture becomes more rapid. If the amount used is less than 0.002%, the effect of the addition is negligible. Over 2.5% the fluidity of the mixture is relatively low, so the workability of the mixture worsens with the same amount of water added and the strength development of the mixture does not increase proportionally with the amount of the amine. 
     Examples of the ethylene glycol series materials include monoethylene glycol, diethylene glycol, triethylene glycol and polyethylene glycol. The amount of the added ethylene glycol material used ranges from 0.02 to 1%, preferably from 0.08 to 0.5%. If the amount used is less than 0.02%, the addition is not effective and even over 1%, the effect does not increase with additional amounts thereof. The ethylene glycol series is effective in increasing the strength over both short range and long periods of time without shortening the handling time of the mixture and is effective in removing the thixotropy of the mixture. 
     The addition of a large amount of the ethylene glycol material does not disturb the workability of the mixture as the amine material does upon mixing with water. 
     Calcium sulphate hemihydrate is added from 0.2 to 5% in such an amount that the ratio of Al 2  O 3  /SO 3  in the cement mixture is from 0.4 to 3.0. If the amount used is less than 0.2%, the effect of the addition is negligible. Over 5%, the addition is not effective because the strength development is disturbed because with additional amounts of hemihydrate the setting time of the mixture increases. 
     The bituminous emulsion to be used in this invention is an emulsion formed by emulsifying a bituminous material in water with at least one member selected from the group consisting of a cationic, anionic, nonionic surface active agent and the clay as a main emulsifier. Acids, alkalis, salts, higher fatty acids, protective colloids or the like can also be used to emulsify the bituminous material in water with the main emulsifier. An acid is used primarily with the cationic and/or nonionic surface active agent. An alkali is used mainly with the anionic and/or nonionic surface active agent, and a salt is used with the cationic, anionic and/or nonionic surface active agent. The higher fatty acid also contributes to the emulsification of the bituminous material. These acids, alkalis, salts, protective colloids, clays or the like may be added to the emulsion to adjust the properties thereof, too. 
     Suitable examples of the bituminous material which are used for the formation of the bituminous emulsion are straight asphalt, blown asphalt, semiblown asphalt, natural asphalt, propane precipitated asphalt, bitumen coal tar, oil tar, pitch, tall oil pitch, fatty acid pitch, heavy oil rubber incorporated bitumen, (rubber dispersed into the above bituminous materials), and resin incorporated bitumen (resin dispersed into the above bituminous materials). 
     An emulsion formed by adding a rubber latex and/or a resin emulsion to the above-mentioned bituminous emulsion may also be used as the bituminous emulsion in this invention. 
     All kinds of emulsions can be made which are mixed homogeneously with the hydraulic material, such as cement and cement mixtures containing cement, an aggregate, a filler or a forming agent, in a chemically and mechanically stable state and so as not to disturb the hydration reaction of the hydraulic materials. 
     The bituminous emulsion contains generally a bituminous material content (evaporated residue) of from 40 to 70% by weight. The penetration at 25° C of the evaporated residue of the bituminous emulsion may be in the range of 10 to 300 generally, too. 
     The known techniques can be applied to the manufacture of the bituminous emulsion. 
     Next, a few examples of the desirable bituminous emulsion are explained. 
     In the cationic emulsion, examples of the cationic emulsifier include mainly higher alkylamines, higher alkyl alkylene polyamines, higher alkyl polyaminoethylene imidazolines, and their polyethoxylated group and a acid salt and quaternary ammonium salt of the above-mentioned amine group, polyaminoimidazoline group. 
     These emulsifiers can be used with a nonionic emulsifier. Acids such as hydrochloric acid, sulfamic acid, acetic acid and the like, and water-soluble salts such the halides of alkali metal and alkaline earth metals and the like may be used with the emulsifier. The examples of the protective colloid are hydroxyethyl cellulose, methyl cellulose, polyvinyl alcohol, gelatin, a salt of lignin amine, a polyoxyethylene polypropylene glycol ether or the like. 
     In an anionic emulsion, examples of the anionic emulsifier include mainly salts of Vinsol resin (a product of Herculess powder Co. Ltd). an alkali salt of casein, a fatty acid soap, an alkali salt of a sulphuric acid ester of higher alcohol, sodium alkylbenzene sulphonate, sodium alkylnaphthalene sulphonate, polyoxyethylene sulphonate and the like. 
     These emulsifiers may be used with the nonionic emulsifier. 
     Alkalis such as NaOH, KOH, NH 4  OH and a water-soluble salt of an alkali metal may be used with the emulsifier. 
     Examples of the protective colloid include carboxymethyl cellulose, mathyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, lignin sulphonate, polyoxyethylene polypropylene glycohol ether and the like. 
     In the above-mentioned nonionic emulsion, examples of the nonionic emulsifier include polyoxyethylene higher alcohol ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene alkyl ethers, glycerin fatty acid esters, propylene glycol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty esters, polyoxyethylene oxypropylene block polymers and the like. The same acid, alkali, salt or protective colloid as used in the cationic emulsion or anionic emulsion may be used with the nonionic emulsion. 
     In a clay type emulsion, examples of the emulsifying agent mainly such as bentonite and the like, and also sometimes a mixture of the clay mentioned above and an anionic or nonionic surface active agent. Acids, alkalis, salts and stabilizing agents which are used with the anionic and cationic emulsion are also used in the clay type emulsion. 
     When the cationic emulsion is used as a bituminous emulsion, the characteristics of the mixture are as follows. For example in a grout type mixture, (1) it is very rare when the mixture of materials is heterogenous in comparison to other mixtures of materials when other types of emulsions are used at the same water cement ratio; (2) the flow time of the mixture at the time just after mixing is short (3) its durability is long (the handling time is long), so the grout type mixture is convenient to pour; (4) the grout type mixture advantageously strengthens the hardened mixture because of the small quantities of water necessary to achieve proper fluidity according to the water-reducing effect of the cationic emulsion; and (5) the long duration of the stress relaxation property is better compared with the other types of emulsions because the tendency of long term strength increases is small. 
     When a nonionic emulsion is used, the characteristics of the mixture are as follows: (1) The short range strength (about 1 to 2 hours after mixing) development of the mixture at low temperature (below about 10° C) is good. (2) The stability against such mechanical stresses as pumping of the mixture is good. (3) The chemical stability against the modifying agents commonly used such as water-reducing agents for cement, dispersing agents, rubber latexes, resin emulsion and the like is good because the nonionic type emulsion can accept a wide range of modifying agents. 
     When the anionic emulsion is used, the characteristics are as follows: (1) Air can be easily entrained on mixing. (2) The emulsion has a water-reducing effect. (3) The tendency of long term strength increases is large. 
     The added amount of the bituminous emulsion is from 0.02 to 3 parts by weight, preferably from 0.15 to 1.5 parts by weight based on the evaporated residue of the emulsion for 1 part by weight of the cement mixture. Under 0.02 parts by weight, the effect of the stress relaxation for the hardened mixture is negligible, and over 3 parts by weight, the strength development of the hardened mixture is not good. 
     The rubber latex or the resin emulsion may be added to the mixture together with the bituminous emulsion to modify the properties of the bituminous materials, too. 
     The examples of the rubber component of the rubber latex to be used in this invention are natural rubber, styrene-butadiene rubber, butyl rubber, styrene-isoprene rubber, acrylonitrilebutadiene rubber, chloroprene rubber and the like. 
     Examples of the resin component of the resin emulsion to be used in this invention are natural resin, polyvinyl acetate, copolymers of ethylene and vinyl acetate, polyvinylidene chloride, resin of polyacrylic acid esters, alkyd resins and the like. The amount of evaporated residue, other properties, the amount to be added to the mixture, the directions for use and the like are almost the same as that of the bituminous emulsion described above. And the mixture of the bituminous emulsion and the rubber latex and/or resin emulsion can be used in the proper ratio. 
     Examples of aggregates and fillers include sand, gravel, rubber powders, grains of resin foam, glass beads, micro balloons, pigments, and short fibers. 
     Examples of the foaming agent are aluminum powder, surface active agents and the like. The surface active agents are used to regulate the density of the mixture by introduction of air foam. 
     To make the mixture of this invention, the short range strength accelerator is added to the super rapid hardening cement and then a bituminous emulsion, a rubber latex and/or a resin emulsion are added to this mixture. If necessary, an aggregate, a filler and a foaming agent are added and then with or without adjustment of the amount of water in the mixture, a set controlling agent. The mixture is mixed well in a mixer. The mixture can be produced by means of a batch process or a continuous process. 
     In the instance when adding a small size of aggregate or filler, because the aggregate or the filler is hard to homogeneously mix with the cement mixture, the mixture is prepared by the following steps: (1) First, the set controlling agent is dissolved in a small amount of water for mixing. (2) Next, the super rapid hardening cement and the short range strength accelerator are added to the solution thus obtained and then mixed until a homogeneous paste-like state is achieved. (3) Then, the sand, the filler, the foaming agent, the bituminous emulsion, the rubber latex and/or the resin emulsion are added to the resulting paste and the mixture obtained is mixed well. 
     When a large size aggregate is used, it is easy to regulate the slump of the mixture by using the bituminous emulsion, the rubber latex and/or the resin emulsion, or by adding the water soluble set controlling agent or the short range strength accelerator previously to these emulsions. 
     The present mixture contains from 12 to 50 weight percent, preferably from 20 to 40 weight percent of water. In the case that the amount of water of the emulsion in the mixture is less than the minimum limits an amount of water sufficient to exceed the lower limit can be added. 
     In this invention, it is easy to shorten or lengthen the handling time of the mixture and also to prepare a hardened mixture having a large short range strength by properly adding a set-controlling agent or a short range strength accelerator to the super rapid hardening cement and by adding a bituminous emulsion, a rubber latex and/or a resin emulsion to the mixture thus obtained. 
     First, a mixture having long handling time characteristics is formed and then just before the placing of the mixture, a short range strength accelerator is added to force the mixture to harden rapidly. It is possible to form a mixture which has excellent stress relaxation, high adhesive and abrasion resistant properties and which exhibits small changes in physical properties with variations in temperature by using a bituminous emulsion modified by mixing a member of the rubber series and/or a member of the resin series or by using a mixture of a bituminous emulsion, a rubber latex and/or a resin emulsion. According to this invention, the rapid hardening properties, the stress relaxation (shock resistance, fatigue resistance), the adhesiveness, the water proofness proof, the sea water resistance, the airtightness, the freezing and thawing resistance, the sound insulating properties, the adiabatic properties, the chemical resistance, the free efflorescence and the like properties of a rapid hardening cement composition are greatly improved. 
     The mixture of this invention can be effectively used in the construction of pavements, floors and the like, in the preparation of cast material such as pipes, blocks, and the like, in the preparation of filling materials such as grouts for ballast-filled track structures and slab-type track structures, as undersealing materials for concrete pavements, and as grouts for the sealed construction of water supplies and drainages, and the like and as a water-proofing treatment and in cut-off materials such as in the stabilization of slopes, the cut-off walls of dams, reservoirs water-ways, roofs and the like. 
     The mixture of the invention can also be used effectively in the creation of new structures in mending operations. Having generally described the invention, a more complete understanding can be obtained by reference to certain specific examples, which are provided herein for purposes of illustration only and are not intended to be limiting unless otherwise specified. 
     The materials used in the examples are as follows: 
     1. Super rapid hardening cement: Two kinds of cement of which the chemical composition and the specific surface area are shown in Table 1. One is &#34;Jet Cement&#34; (manufactured by Onoda Cement Co. Ltd.) which contains 20.6 percent of 11CaO.7Al 2  O 3 .CaF 2   and the other is a cement which contains 31.1 percent of 11CaO.7Al 2  O 3 .CaF 2 . 
     2. Tartaric acid, citric acid, gluconic acid, boric acid, sodium carbonate and potassium carbonate are readily available industrial chemicals. 
     3. Calcium aluminate: Two kinds of calcium aluminate of which the chemical composition, and the specific surface area are shown in Table 1. One aluminate (calcium aluminate I) was manufactured by Asahi Glass Co., Ltd. and the other aluminate (calcium aluminate II) was manufactured by burning a powdered mixture of bauxite having the chemical composition shown in Table I in an electric furnace for 3 hours at a temperature of 1350° C and by pulverising the clinker thus obtained to a specific surface area of 4300 cm 2  /g. The principal constituent of the calcium aluminate consists of 12CaO. 7Al 2  O 3 . 
     4. Calcium hydroxide, triethanolamine, diethylene glycol and calcium sulphate hemihydrate are readily available industrial chemicals. 
     5. Quick lime: Limestone was burnt at 1400° C for 3 hours and pulverized to a specific surface area of 3200 cm 2  /g and has the chemical composition shown in Table I. 
     
                                           Table I                                 
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Component                        Specific                                 
        SiO.sub.2                                                         
           Al.sub.2 O.sub.3                                               
               Fe.sub.2 O.sub.3                                           
                   CaO MgO                                                
                          SO.sub.3                                        
                             Ig.loss                                      
                                 surface                                  
Material                                                                  
        %  %   %   %   %  %  %   m.sup.2 /g                               
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Rapid                                                                     
hardening                                                                 
        13.8                                                              
           11.4                                                           
               1.5 59.1                                                   
                       0.9                                                
                          10.2                                            
                             0.1 5,650                                    
cement I                                                                  
(Jet Cement)                                                              
Rapid                                                                     
hardening                                                                 
        8.2                                                               
           16.9                                                           
               1.8 53.8                                                   
                       0.6                                                
                          17.0                                            
                             0.3 4,970                                    
cement II                                                                 
Calcium                                                                   
aluminate I                                                               
        3.0                                                               
           40.0                                                           
               16.9                                                       
                   38.7                                                   
                       0.4                                                
                          -- 1.0 3,290                                    
(Aluminous                                                                
Cement)                                                                   
Calcium                                                                   
aluminate II                                                              
        2.5                                                               
           43.3                                                           
               1.5 51.0                                                   
                       0.6                                                
                          -- 1.1 4,300                                    
Quick lime                                                                
        0.5                                                               
           0.1 0.6 97.7                                                   
                       0.8                                                
                          -- 0.1 3,200                                    
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     6. Bituminous emulsion: 
     i. Cationic asphalt emulsion (will be referred to as a C-1, hereinafter: The emulsion was made by emulsifying a straight asphalt (penetration 80 ˜ 100) with an emulsifier mainly consists of higher alkyl (hydrogenated tallow) trimethyl ammonium chloride. Its properties are shown in Table II. 
     ii. Nonionic asphalt emulsion (will be stated as only N-1, hereafter): The emulsion was made by emulsifying a straight asphalt (penetration at 25° C, 90) with an emulsifier which consists mainly of polyoxyethylene nonylphenol ether (HLB ≈ 14). The properties of the emulsion are shown in Table II. 
     iii. Anionic asphalt emulsion modified by rubber emulsion (will be referred to hereinafter as LA-1): The emulsion was made by emulsifying the straight asphalt with an emulsifier of which the main emulsifying agent is a sodium salt of Vinsole resin and mixed with a styrene-butadiene rubber latex (45% nonvolatile content) in a ratio of 0.1 as the solid rubber to the evaporated residue of the asphalt emulsion. The properties of the emulsion are shown in Table II. 
     
                       Table II                                                    
______________________________________                                    
Properties of Bituminous Emulsion                                         
                                        Penetra-                          
                                        tion                              
                                        of                                
                 Viscosity                                                
                          Mixing Evapor-                                  
                                        evapor-                           
                 (degree  property                                        
                                 ated   ated                              
Kinds of                                                                  
       Charge of Engler   with   residue                                  
                                        residue                           
emulsion                                                                  
       particle  at 25° C                                          
                          cement (wt.%) at 25° C                   
______________________________________                                    
C - 1  (+)       5.8      pass   59.6   98                                
N - 1            6.5      pass   59.3   95                                
LA - 1 (-)       6.2      pass   59.1   93                                
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     7. Rubber latex: A chloroprene rubber latex whose solid percentage is 50% is a readily available commodity industrial. 
     Resin emulsion: An emulsion of a polyacrylic acid ester having a solid percentage of 45% is a readily available industrial commodity. 
     8. Sand: Sand from the river Fujigawa, Shizuoka prefecture, Japan, having particle size under 2.5 mm, a fineness modulus of 1.6, and a density of 2.60 g/cm 3  was used. 
     Gravel: Gravel from the river Fujigawa, having a particle size under 25 mm, and a density of 2.61 g/cm 3  was used. 
     9. Rubber powder: A readily available rubber was used having a particle size under 2.5 mm, and a fineness modulus of 2.2. 
     10. Water: Normal tap. 
     11. Aluminum powder: manufactured by Nakashima Metal Foil and Powder Co., Ltd., for cement C-300. 
     12. High early strength cement: manufactured by Onoda Cement Co., Ltd., and having a chemical composition as follows: 
     
         ______________________________________                                    
                                          Specific                        
Ig. loss                                                                  
      SiO.sub.2                                                           
             Al.sub.2 O.sub.3                                             
                     Fe.sub.2 O.sub.3                                     
                           CaO  MgO  SO.sub.3                             
                                          surface                         
%     %      %       %     %    %    %    area (g/cm.sup.2)               
______________________________________                                    
0.9   20.7   5.0     2.7  65.9  1.3  2.4  4,240                           
______________________________________                                    
 
    
     The mixing procedure used in the example is as follows: The set controlling agent was dissolved in water, and a super rapid hardening cement and a short range strength accelerator were mixed in the mixer (revolutions 100 r.p.m.) for 1 minute (from this, the time was counted from this point). 
     An aggregate was added in the mixture with or without a foaming agent which was then an emulsion are added to the resulting mixture and mixed for 2 minutes. Then the mixing was continued in the mixer at the speed of 40 r.p.m.. 
     
                                           Table III                               
__________________________________________________________________________
(Weight Part)                                                             
       Rapid                                                              
       Hardening                                                          
       cement                                                             
             Short Range                                                  
          Ra-                                                             
             Strength Accelerator                                         
                              Set                                         
          pid       Cal-      Controlling             Foam-               
          hard-                                                           
             Cal-       cium            Agent             ing             
Temp.     en-                                                             
             cium   Sul-   Di-       So-              agent               
of        ing                                                             
             alu-   fate                                                  
                        Tri-                                              
                           eth-      dium             Alum-               
                                                          Added           
mixing Jet                                                                
          ce-                                                             
             min-   hemi-                                                 
                        etha-                                             
                           ylen   Bor-                                    
                                     car-                                 
                                        Bituminous    inium               
                                                          Amount          
and    ce-                                                                
          ment                                                            
             ate                                                          
                Slaked                                                    
                    hy- nola-                                             
                           gly-                                           
                              Citric                                      
                                  ic bon-                                 
                                        emulsion      pow-                
                                                          of              
No.                                                                       
   Curing                                                                 
       ment                                                               
          II I  lime                                                      
                    drate                                                 
                        mine                                              
                           col                                            
                              acid                                        
                                  acid                                    
                                     ate                                  
                                        C-1 N-1 LA-1                      
                                                   Sand                   
                                                      der Water           
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1  5   69.7  24 6             0.12   0.18                                 
                                        100        100    43              
2  20  69.0  24 6             0.4    0.6                                  
                                        100        100    40              
3  20  99.75               0.1                                            
                              0.15      100        100                    
                                                      0.01                
                                                          40              
4  20  98.0         1.5 0.4   0.1       100        100                    
                                                      0.01                
                                                          40              
5  20  98.8             1.0       0.1                                     
                                     0.1                                  
                                        100        100                    
                                                      0.01                
                                                          45              
6  20  98.15        1.5    0.2                                            
                              0.15              100                       
                                                   100                    
                                                      0.01                
                                                          40              
7  20  98.25        1.5       0.05                                        
                                  0.2       100    100                    
                                                      0.01                
                                                          43              
8  5      99.0      0.5              0.5                                  
                                        100        100                    
                                                      0.01                
                                                          40              
9  20  97.8         2.0 0.1   0.1       100               40              
a  20  100.0                            100        100                    
                                                      0.01                
                                                          38              
b  20  99.85                  0.15          100*   100                    
                                                      0.01                
                                                          45              
__________________________________________________________________________
 Note:                                                                    
 1) No. a shows a sample number of a comparative example.                 
 2) No. b shows a sample number of a comparative example.                 
 3) *is a emulsion manufactured by Toa Doro Kogyo Co., Ltd.               
 
    
    
    
     EXAMPLE 1 
     Various mixtures corresponding to sample Nos. 1 to 9 and the comparative examples a and b having the mixing ratios shown in Table III were made. 
     EXAMPLE 2 
     Various mixtures corresponding to sample Nos. 10 to 14 having various fluidity values and the mixing ratios shown in Table IV were made. 
     
                       Table IV                                                    
______________________________________                                    
(Weight Part)                                                             
                    Cal-                                                  
                    cium  Tri-                                            
     Mixing         Sul-  eth-                                            
     temp-          fate  an-                  Added                      
     era-    Jet    hemi- ol                   amount                     
     ture    ce-    hy-   a-             Boric of                         
No.  (° C)                                                         
             ment   drate mine C-1  Sand acid  water                      
______________________________________                                    
10   20      98.1   1.5   0.4  100  100  0.05  40                         
11   20      98.1   1.5   0.4  100  100  0.1   40                         
12   20      98.1   1.5   0.4  100  100  0.2   40                         
13   20      98.1   1.5   0.4  100  100  0.4   40                         
14   20      98.1   1.5   0.4  100  100  0.8   40                         
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     The change of the fluidity of the mixture with time is shown in the figure. The figure shows the relation between the flow time of the super rapid hardening mixture made in Example 2 and the mixing time. The fluidity was measured by the J-funnel test according to the specifications for the execution of prepacked concrete proposed by the Japanese Society of Civil Engineers. 
     EXAMPLE 3 
     Various mixtures were formulated according to the proportions shown in Table V. After 15 or 60 minutes, 10 parts of quick lime were added to the mixture to formulate mixtures. 
     
                       Table V                                                     
______________________________________                                    
(Weight Part)                                                             
     Tempera-                                                             
     ture                                  Added                          
     of mixing                             amount                         
     and curing                                                           
               Jet     Bituminous   Tartaric                              
                                           of                             
No.  (° C)                                                         
               cement  emulsion                                           
                               Sand acid   water                          
______________________________________                                    
15   5         89.8    C - 1   100  0.2    40                             
                       100                                                
16   5         89.8    LA - 1  100  0.2    40                             
                       100                                                
17   5         89.8    N - 1   100  0.2    40                             
                       100                                                
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     Test pieces were made from the mixture thus prepared and the strength of the hardened mixtures was measured. The results are shown in Table VI. 
     EXAMPLE 4 
     Various mixtures having large stress relaxation were mixed and made according to the proportions of sample Nos. 18 and 19 shown in Table VII. 
     
                       Table VI                                                    
______________________________________                                    
                        Compres-                                          
                        sive                                              
         Flow time      strength  Elastic                                 
Mixing   (second)       (kg/cm.sup.2)                                     
                                  modulus after                           
     time    Just after                                                   
                      After quick  28   28 days                           
No.  (min.)  mixed    lime mixed                                          
                              1 hr*                                       
                                   days (kg/cm.sup.2)                     
______________________________________                                    
15   15      6.2      6.7     7.5  53.2 6,700                             
     60      6.3      7.2     7.9  55.0 6,900                             
16   15      6.7      7.4     6.3  58.0 7,600                             
     60      6.7      7.6     6.8  58.9 7,500                             
17   15      6.8      7.4     7.6  58.0 7,800                             
     60      6.7      7.7     8.1  59.0 8,200                             
______________________________________                                    
 Note:                                                                    
 1) The testing method is the same as that in Table XI foot note (1).     
 2) *shows the time after quick lime was mixed.                           
 
    
     
                       Table VII - 1                                               
______________________________________                                    
(Weight Part)                                                             
     Temperature                                                          
     of mixing and          Calcium Quick                                 
No.  curing (° C)                                                  
                  Jet cement                                              
                            aluminate                                     
                                    lime                                  
______________________________________                                    
18   20           98.7      8       2*                                    
19   20           99.0      18      2**                                   
______________________________________                                    
 
    
     
                       Table VII - 2                                               
______________________________________                                    
(Weight Part)                                                             
                                         Added                            
     Gluconic Potassium           Rubber amount                           
No.  acid     carbonate C - 1                                             
                             Sand powder of water                         
______________________________________                                    
18   0.5      0.8       125       30     35                               
19   0.4      0.6       150  100         45                               
______________________________________                                    
 Note:                                                                    
 *shows 2 parts of quick lime.                                            
 **shows 2 parts of slaked lime.                                          
 
    
     EXAMPLE 5 
     Ten parts of chloroprene rubber latex were added to the mixture which was made by mixing raw materials in the proportions of sample No. 20 shown in Table VIII. A mixture modified by rubber was made. 
     
                       Table VIII - 1                                              
______________________________________                                    
(Weight Part)                                                             
     Temperature            Calcium                                       
     of mixing              sulfate    Citric                             
No.  and curing (° C)                                              
                  Jet cement                                              
                            hemihydrate                                   
                                       acid                               
______________________________________                                    
20   20           98.85     1.0        0.15                               
______________________________________                                    
 
    
     
                       Table VIII - 2                                              
______________________________________                                    
(Weight Part)                                                             
                      Aluminum   Added amount                             
No.   N - 1   Sand    powder     of water                                 
______________________________________                                    
20    90      100     0.01       40                                       
______________________________________                                    
 
    
     EXAMPLE 6 
     The mixture having large stress relaxation were mixed according to the proportions of sample No. 21 and comparative sample No. c shown in Table IX. 
     EXAMPLE 7 
     Mixtures characterized by large stress relaxation were formulated and mixed according to the proportions of sample Nos. 22 and 23 and comparative sample No. d shown in Table X. 
     
                       Table IX                                                    
______________________________________                                    
(Weight Part)                                                             
     Temp-                                                                
     era-           Cal-                                                  
     ture           cium                                                  
     of             sul-       Tri-                                       
     mixing         fate       eth-            Added                      
     and     Jet    hemi- Ci-  an-             amount                     
     curing  ce-    hy-   tric ol-a-           of                         
No.  (° C)                                                         
             ment   drate acid mine  Sand C-1  water                      
______________________________________                                    
21   20      98.1   1.5   0.2  0.2   200  150  0                          
c    20       100*             200  150  0                                
______________________________________                                    
 Note:?                                                                   
 1) No. c is a sample of a comparative example.                           
 2) *shows 100 parts of high early strength Portland cement.              
 
    
     
                       Table X - 1                                                 
______________________________________                                    
(Weight Part)                                                             
     Temp-                                                                
     era-                 Cal-                                            
     ture                 cium  Di-                                       
     of             Cal-  sul-  eth-        Potas-                        
     mixing         cium  fate  yl-         sium                          
     and     Jet    alu-  hemi- ene         car-                          
     curing  ce-    min-  hy-   gly-  Citric                              
                                            bon-                          
No.  (° C)                                                         
             ment   ate   drate col   acid  ate                           
______________________________________                                    
22   20      95.9         4           0.1                                 
23   20      79.2   19    1     0.1   0.4   0.3                           
d    20       100*                                                        
______________________________________                                    
 Note:                                                                    
 1) No. d shows a sample number of a comparative example.                 
 2) *shows 100 parts of high early strength Portland cement.              
 
    
     
                       Table X - 2                                                 
______________________________________                                    
(Weight Part)                                                             
                                   Added                                  
      Bituminous                   amount                                 
No.   emulsion    Sand   Aggregate of water                               
______________________________________                                    
22    C - 1       200    400       35                                     
      50                                                                  
23    N - 1       200    400       37                                     
      50                                                                  
d     C - 1       200    400       32                                     
      50                                                                  
______________________________________                                    
 Note:                                                                    
 1) No. d shows a sample number of a comparative example.                 
 2) *shows 100 parts of high early strength Portland cement.              
 
    
     Physical tests of the mixture of the super rapid hardening cement and the bituminous emulsion and of the hardened mixture of examples 1, 4, 5, 6 and 7 were conducted and the results are shown in Table XI. Also, the results of the physical tests of comparative example Nos. a, b, c and d are shown in the same table. 
     
                                           Table XI                                
__________________________________________________________________________
        Fluidity         Compressive strength                             
                                      Elastic                             
        (Just after mixing)                                               
                         (kg/cm.sup.2)                                    
                                      modulus                             
        Flow                                                              
            Flow    Handling          (after                              
        time                                                              
            value                                                         
                Slump                                                     
                    time 1 1.5                                            
                             3  24 28 28 days)                            
Example                                                                   
     No.                                                                  
        (sec)                                                             
            (mm)                                                          
                (cm)                                                      
                    (min)                                                 
                         hr                                               
                           hrs                                            
                             hrs                                          
                                hrs                                       
                                   days                                   
                                      kg/cm.sup.2                         
__________________________________________________________________________
1    1  6.2         20   4.0                                              
                           6.2  19.8                                      
                                   48.2                                   
                                      6,300                               
     2  5.7         20   3.9                                              
                           6.0  28.7                                      
                                   65.3                                   
                                      8,200                               
     3  6.0         22   3.6                                              
                           6.2  15.1                                      
                                   62.9                                   
                                      7,800                               
     4  6.8         19     9.1  36.9                                      
                                   79.7                                   
                                      10,200                              
     5  6.4         21     8.5  29.0                                      
                                   64.1                                   
                                      7,500                               
     6  6.2         22     5.3  23.4                                      
                                   69.4                                   
                                      8,700                               
     7  6.3         20     6.9  28.2                                      
                                   72.0                                   
                                      9,600                               
     8  7.2         19     6.4  33.0                                      
                                   58.6                                   
                                      7,000                               
     9  4.7         23     9.7  41.5                                      
                                   75.6                                   
                                      6,800                               
     a  7.0         210          2.0                                      
                                   47.5                                   
                                      7,100                               
     b  7.4         15     2.7                                            
                             4.8                                          
                                24.6                                      
                                   60.4                                   
                                      6,200                               
4    18 7.2         35       4.4                                          
                                12.4                                      
                                   22.7                                   
                                      2,800                               
     19 5.7         20   2.3 6.1                                          
                                11.9                                      
                                   32.0                                   
                                      4,500                               
5    20 6.8         32     6.5  30.6                                      
                                   52.8                                   
                                      5,800                               
6    21     231     18       2.8                                          
                                 7.7                                      
                                   31.1                                   
     c      223     215          1.5                                      
                                   23.2                                   
     22         21.1                                                      
                    57       44.1                                         
                                157                                       
                                   236                                    
7    23         21.8                                                      
                    64       40.2                                         
                                155                                       
                                   270                                    
     d          21.4                                                      
                    315         59.4                                      
                                   147                                    
__________________________________________________________________________
 Note:                                                                    
 1) The tests conducted were in accordance with the procedure established 
 for the execution of prepacked concrete (edited by Japanese Society of   
 Civil Engineers), JIS A-1101; JIS A-1108; JIS A-1132; JIS A-5201. The    
 loading speed of the strength tests and the measurement of the modulus of
 elasticity was 1 mm/min.                                                 
 2) The handling time for the examples 1, 4 and 5 is the time which elapse
 until the flow time reaches 10 seconds. The handling time in examples 6  
 and 7 is the time which elapses until the setting starts.                
 3) Modulus of elasticity is the scant modulus of elasticity of the       
 specimen diameter 50× height 100 mm at the stress of 4 kg/cm.sup.2.
 
    
     EXAMPLE 8 
     An anionic asphalt emulsion (evaporated residue, 59.8%, penetration at 25° C, 95) was made by emulsifying straight asphalt (penetration at 25° C, 92) with a polyoxyethylene oleyl ether (HLB ≈ 14.5) and sodium dodecylbenzen sulphonate, and was used in the formulation of the following mixture. 
     The proportions of the mixture are as follows: (part by weight) 
     
         ______________________________________                                    
                        The above      Added                              
Slaked                                                                    
      Citric  Sodium    asphalt        amount                             
lime  acid    carbonate emulsion Sand  of water                           
______________________________________                                    
6     0.4     0.6       280      100   0                                  
______________________________________                                    
 
    
     It was found from the results of the tests shown in the Figure, Table VII and XI that the mixtures of this invention possess excellent properties. Compressive strength of from 6 to 10 kg/cm 2 , (90 minutes after mixing) were obtained in Example 1, samples Nos. 1 to 9. However, the compressive strength of the hardened mixture of comparative sample No. a was zero (90 minutes after mixing). 
     The compressive strength of the hardened mixture, (one day after mixing) of Example 1 was from 10 to 20 times higher than that of comparative sample No. a. 
     The strength development of the hardened mixtures of this invention at low temperature (5° C) was the same as that at ordinary temperatures as shown in samples Nos. 1 and 8 of Example 1. 
     As shown by samples No. 10 to 14 of Example 2, mixtures were obtained whose handling time is freely controllable. The mixtures have good fluidity and develop substantial strength in a the short range of time. As shown in samples No. 15 to 17 of Example 3, the mixtures having long handling time are obtained. It is therefore possible to transport the mixture by means of a pump and to force it to harden, or the mixture can be forced to harden rapidly by adding one component to the mixture just before pouring. 
     Mixtures having large stress relaxation and of the small elastic modulus are obtained by using rubber powder as an aggregate as shown in Example 4, sample No. 18. The same effect as that in sample No. 18 was obtained by increasing the amount of the emulsion added in sample No. 19. The same effect as that in sample No. 18 was proved in the sample No. 20 of Example 5, by adding the rubber latex to the mixture. 
     The results of Example 6 and 7 show that the mixture of this invention gives markedly high strength earlier than the comparative samples. 
     The mixture obtained in Example 8 gave a compressive strength of 2.1 kg/cm 2  after 180 minutes of curing just like as in Example 1. 
     EXAMPLE 9 
     A mixture was formulated and mixed according to the proportions of sample No. 24 shown in Table XII. The ambient temperature of mixing was 20° C. 
     
                       Table XII                                                   
______________________________________                                    
(Weight Part)                                                             
            Cal-                                                          
            cium                                                          
            sul-                                                          
            fate                             Added                        
     Jet    hemi-                            amount                       
     ce-    hy-     Citric                                                
                          Rubber     Aluminum                             
                                             of                           
No.  ment   drate   acid  latex Sand powder  water                        
______________________________________                                    
24   98.35  1.5     0.15  30    100  0.01    50                           
______________________________________                                    
 
    
     The flow time of this mixture just after mixing was 6.5 seconds and the strength of the hardened mixture is shown in Table XIII. 
     
                       Table XIII                                                  
______________________________________                                    
Compressive strength (kg/cm.sup.2)                                        
______________________________________                                    
1 hr        3 hrs         28 days                                         
18.7        104           228                                             
______________________________________                                    
 
    
     EXAMPLE 10 
     The mixture was formulated mixed according to the proportions of sample No. 25 in Table XIV. 
     The mixing temperature was 20° C. 
     
                       Table XIV                                                   
______________________________________                                    
(Weight Part)                                                             
            Cal-                                                          
            cium                                                          
            sul-                                                          
            fate                             Added                        
     Jet    hemi-         Resin              amount                       
     ce-    hy-     Citric                                                
                          emul-      Aluminum                             
                                             of                           
No.  ment   drate   acid  sion  Sand powder  water                        
______________________________________                                    
25   98.35  1.5     0.15  100   100  0.01    40                           
______________________________________                                    
 
    
     The flow time of this mixture just after mixing was 5.5 seconds and the strength of the hardened mixture is shown in Table XV. 
     
                       Table XV                                                    
______________________________________                                    
Compressive strength (kg/cm.sup.2)                                        
______________________________________                                    
1 hr             28 days                                                  
6.5              75                                                       
______________________________________