阅读说明：本技术 宏观水泥组合物、宏观水泥的生产方法和宏观水泥的工程化形式以及制备胶结材料的多级均质工艺 (Macroscopic cement composition, method for producing macroscopic cement, engineered form of macroscopic cement and multistage homogenization process for preparing cementitious material ) 是由 亚历山大·奥泽斯凯 亚历山大·科米克洛夫 于 2018-02-23 设计创作，主要内容包括：本发明公开了可用于制备具有高可加工性、高密度和高强度的浆料、砂浆、混凝土和其他胶结材料的宏观水泥及其相关方法。生产宏观水泥的方法包括水泥、包括硅质亚微米级颗粒和纳米级颗粒的补充胶凝材料(SCM),以及用于混凝土的液体或干粉化学外加剂形式的聚合物。该水泥混合物可用于制备超高性能混凝土(UHPC)。(Macroscopic cements useful for making slurries, mortars, concretes and other cementitious materials having high workability, high density and high strength and related methods are disclosed. The method of producing macroscopic cements comprises cement, Supplementary Cementitious Materials (SCM) comprising siliceous submicron and nanoscale particles, and a polymer in the form of a liquid or dry powder chemical admixture for concrete. The cement mixture can be used for preparing Ultra High Performance Concrete (UHPC).)

1. A multi-component macroscopic cement composition, comprising:

a cementitious material comprising micron-sized particles; and

a Supplementary Cementitious Material (SCM) of submicron or nanoscale particles or a combination thereof coated or supported on said cementitious material.

2. The composition of claim 1 wherein the cementitious material further comprises a micro-sized particulate pozzolanic material.

3. The composition of claim 1 or 2, further comprising an aggregate.

4. The composition of claims 1-3, further comprising a reinforcing fiber.

5. The composition of claims 1-4, further comprising a binder.

6. The composition of claims 1-5, wherein the composition is produced in the form of granules, pellets, briquettes, or tablets.

7. The composition of claim 1 wherein the cementitious material is portland cement, fly ash (class C as received), or slag (ground blast furnace dust).

8. The composition of claim 2, wherein the pozzolanic material is fly ash (class F as such), coarse metakaolin, or calcined clay.

9. The composition according to claim 1, wherein the SCM is siliceous-SiO-containing₂The particles of (1).

10. The composition of claim 9, wherein the siliceous-SiO-containing composition₂The particles of (A) are silica powder, quartz (fine powder), precipitated silica, fly ash (fine powder), metakaolin or rice hull ash.

11. The composition according to claim 1, wherein the SCM is nanosilica, carbon nanotubes and nanofibers, nano-TiO₂Or nano Fe₂O₃A nanoclay.

12. The composition of claim 5, wherein the binder is a polymer in the form of a liquid or powdered chemical additive.

13. The composition of claim 12, wherein the additive is a superplasticizer/high range water reducer, a plasticizer/mid and normal range water reducer, and/or a retarding or accelerating admixture for concrete.

14. The composition of claim 1, wherein the SCM is secured to the cementitious material by dry coating without the use of an adhesive.

15. The composition of claim 3, wherein the aggregate is a fine aggregate.

16. The composition of claim 15, wherein the fine aggregate is natural or synthetic sand, quartz, or bauxite.

17. The composition of claim 15, further comprising a coarse aggregate.

18. The composition of claim 17, wherein the coarse aggregate is gravel, crushed stone, recycled concrete, or a geosynthetic aggregate.

19. The composition of claim 18, wherein the crushed stone is limestone, basalt, granite, or bauxite.

20. The composition of claim 4, wherein the reinforcing fibers are metal fibers, glass fibers, synthetic fibers, or natural fibers, including but not limited to cellulose and hemp fibers.

21. The composition of claim 20, wherein the metal fibers comprise any one of steel, stainless steel, titanium, copper, or brass clad steel.

22. The composition of claim 20, wherein the synthetic fibers comprise polypropylene, carbon fibers, or aramid fibers.

23. The composition of claim 20, wherein during dry coating and/or loading of macroscopic cement, the reinforcing fibers are crushed by the aggregate to provide a scraping surface thereon, and wherein the scraping surface contains particles of the composition.

24. The composition of claim 1, wherein the composition is produced in the form of granules, pellets, briquettes, or tablets during coating and/or loading of the cementitious material by mechanical activation.

25. The composition of claim 24, wherein the activation comprises pressure and shear forces that cause the cementitious material to activate.

26. A method of producing a multi-component macroscopic cement comprising coating or supporting micro-sized particles of a cementitious material with a Supplementary Cementitious Material (SCM) of sub-micron or nano-sized particles or a combination thereof.

27. The method of claim 26, further comprising adding micro-sized particles of a pozzolanic material to the cementitious material prior to the coating or loading.

28. The method of claim 26 or 27, further comprising adding aggregate in the macro cement prior to the coating or loading.

29. The method of claims 26-28, further comprising adding reinforcing fibers in the macroscopic cement prior to the coating or loading.

30. The method of claims 26-29, further comprising utilizing an adhesive.

31. The method of claims 26-30, further comprising engineering the multi-component macroscopic cement by preparing the multi-component macroscopic cement as particles, pellets, agglomerates, or pieces.

32. The method of claim 26 wherein the cementitious material is portland cement having about 250m²/kg to about 750m²A fineness of blaine/kg, corresponding approximately to 10% of the diameter d₁₀0.7 μm to about 90% diameter d₉₀Particle size 70 μm.

33. The method of claim 32, wherein the portland cement has a thickness of about 350m²/kg to about 550m²A fineness of blaine/kg of aboutCorresponds to about d₁₀1 μm to about d₉₀Particle size 50 μm.

34. The method of claim 26 wherein the cementitious material is calcium aluminate cement.

35. The method of claim 26, wherein the cementitious material is fly ash (class C) having an approximate fineness of retention on 45 μ ι η rejects of about 5% to 45%, corresponding about to about d₁₀1 μm to about d₉₀Particle size 50 μm.

36. The method of claim 26 wherein the cementitious material is slag (ground blast furnace dust) having about 250m²Kg to about 600m²A fineness of blaine/kg, corresponding approximately to 10% of the diameter d₁₀1 μm to about 90% diameter d₉₀Particle size 70 μm.

37. The method of claim 27, wherein the pozzolanic material is fly ash (class F) having an approximate fineness retained on a 45 μ ι η rejects of about 5% to 45%, corresponding about to about d₁₀1 μm to about d₉₀Siliceous particles of particle size 50 μm.

38. The method of claim 26, wherein the sub-micron particles have a SCM of 5000m²Kg to 200000m²Silicon powder (microsilica) with a specific surface area of/kg.

39. A process according to claim 38, wherein the silicon powder more specifically has a particle size of 15000m²/kg to 30000m²A specific surface area per kg, or typically about 10nm (nanometers) to 1 μm.

40. The method according to claim 26, wherein the amount of SCM is 5-50% by weight of cementitious material.

41. The method according to claim 40, wherein the SCM is in an amount of 20-40% by weight of cementitious material.

42. The method according to claim 26, wherein the SCM particles are in the size range of 1-100 nm.

43. The method as recited in claim 42, wherein the SCM particles comprise nanosilica, carbon nanotubes and fibers, nanoclay, nano-TiO₂Nano Fe₂O₃Or other nano-sized SCM particles.

44. The method of claim 43, wherein the amount of nanosilica is from 0.25-10% by weight of the macroscopic cement.

45. The method of claim 44, wherein the amount of nanosilica is 1-5% by weight of the macroscopic cement.

46. The method of claim 45, wherein the amount of nanosilica is 2-3% by weight of the macroscopic cement.

47. The method of claim 43, wherein the amount of carbon nanotubes and fibers is 0.003-1% by weight of the macrocement.

48. The method of claim 47, wherein the amount of carbon nanotubes and fibers is 0.01-0.5% by weight of the macrocement.

49. The method of claim 48, wherein the amount of carbon nanotubes and fibers is 0.05-0.1% by weight of the macrocement.

50. The method of claim 43, wherein the nano TiO₂The amount of the cement is 0.01 to 10 percent of the weight of the macroscopic cement。

51. The method of claim 50, wherein the nano TiO₂In an amount of 1-5% by weight of the macroscopic cement.

52. The method of claim 43, wherein the nano-Fe₂O₃The amount of (B) is 0.01-10% of the weight of the macroscopic cement.

53. The method of claim 52, wherein the nano-Fe₂O₃In an amount of 3-5% by weight of the macroscopic cement.

54. The method of claim 30, wherein the binder is a polymer in the form of a liquid or powdered chemical additive.

55. The method of claim 30 wherein the binder is a polymer in the form of a liquid chemical admixture for concrete.

56. The method of claim 55, wherein the polymer comprises water reducing, set retarding, binding and other admixtures for concrete.

57. The method of claim 56, wherein the water-reducing polymer is a superplasticizer.

58. The method of claim 57, wherein the superplasticizer is a melamine or naphthalene or polycarboxylate.

59. The method of claim 56, wherein the amount of superplasticizer is from 0.1 to 10% by weight of the macroscopic cement.

60. The method of claim 59, wherein the amount of superplasticizer is from 0.5 to 5% by weight of the macroscopic cement.

61. The method of claim 60, wherein the amount of superplasticizer is from 1 to 2.5% by weight of the macrocement.

62. The method of claim 56, wherein the retarding admixture comprises any one of: lignin, borax, sugar, organic phosphate, tartaric acid and salts, sodium gluconate and sodium glucoheptonate, sodium phosphate and zinc salts.

63. The method of claim 56, wherein the amount of the set retarding admixture is from 0.05 to 0.5 percent by weight of the macroscopic cement.

64. The method of claim 56, wherein the bonding admixture comprises any one of polyvinyl chloride, polyvinyl acetate, acrylic, and butadiene-styrene copolymer.

65. The method of claim 26, wherein the coating is performed by adhesive-free dry coating under conditions of strong mechanical force.

66. The method of claim 26, wherein the loading is performed under conditions of strong mechanical force by dry coating with an adhesive.

67. The method of claim 65 or 66, wherein said strong mechanical forces comprise impact, compression and shear forces exerted on said particles, resulting in collisions of particles with each other and repeated compression/shear deformation of a continuum of particles.

68. The method of claim 28, wherein the aggregate is a fine aggregate.

69. The method of claim 68, wherein the fine aggregate is natural or synthetic quartz or bauxite sand.

70. The method of claim 68, further comprising coarse aggregate.

71. The method of claim 70, wherein the coarse aggregate is gravel, crushed stone, recycled concrete, or a geosynthetic aggregate.

72. The method of claim 71, wherein the crushed stone is limestone, basalt, granite, or bauxite.

73. The method of claim 29, wherein the reinforcing fibers are metal fibers, glass fibers, synthetic fibers, or natural fibers, including but not limited to cellulose and hemp fibers.

74. The method of claim 73, wherein the metal fibers comprise any one of steel, stainless steel, titanium, copper, or brass clad steel.

75. The method of claim 73, wherein the synthetic fibers comprise polypropylene, carbon fibers, or aramid fibers.

76. The method of claim 73, wherein during dry coating and/or loading of the macroscopic cement, the reinforcing fibers are crushed by the aggregate to provide a scraping surface thereon, and wherein the scraping surface contains particles of the composition.

77. The method of claim 26, wherein the macroscopic cement is produced in the form of particles, pellets, agglomerates, or sheets during the coating and/or loading of the cementitious material by mechanical activation.

78. The method of claim 77, wherein the activation comprises pressure and shear forces that cause physicochemical activation of the cementitious material.

79. The method of claim 78, wherein the particles are produced directly during the coating and/or loading of the cementitious material into an apparatus performing the coating and/or loading process, the particles having a somewhat rounded or somewhat rounded and flattened shape and an equivalent spherical diameter of about 1 to about 20 mm.

80. A process as claimed in claim 78, in which the granules are produced in tumbling drums and pans, fluidised beds and mixing granulators, after the cementitious material coating and/or loading process, the granules having a slightly rounded or slightly rounded and flattened shape and an equivalent spherical diameter of about 1 to about 5 mm.

81. A process as claimed in claim 78, in which the granules are produced in a tumbling drum and pan, fluidised bed and mixer granulator after the cementitious material coating and/or loading process, the granules having a somewhat rounded or somewhat rounded and flattened shape and an equivalent spherical diameter of from about 2 to about 10 mm.

82. The method of claim 78, wherein the pellets are produced by extrusion in an extruder or pelletizer after the coating and/or loading process of the cementitious material, the pellets having a cylindrical shape and an equivalent spherical diameter of about 5 to about 40 mm.

83. The method of claim 78 wherein after the cementitious material coating and/or loading process, the mass or sheet is produced by compression at a roller with shaped voids, the mass or sheet having a slightly rounded or rectangular shape and an equivalent spherical diameter of about 10 to about 50 mm.

84. The method of claim 78 wherein after the cementitious material coating and/or loading process, the agglomerates are produced by compression from smooth rolls, the agglomerates having an irregular fractured zone shape and an equivalent spherical diameter of about 3 to about 30 mm.

85. A method of producing a cement-based material using multi-stage homogenization, comprising:

producing a multi-component macroscopic cement by coating or supporting micro-sized particles of a cementitious material with sub-micron or nano-sized particles or a combination thereof of a Supplementary Cementitious Material (SCM);

injecting the macroscopic cement into a strongly moving energized water stream;

producing a first mixture by homogenizing a water stream with a macroscopic cement in an intensive homogenizer, the energy density of which is sufficient to overcome the cohesion of the macroscopic cement, to substantially completely disperse and homogenize without separating the multi-component macroscopic cement and water;

directing the first mixture into a second mixer having a lower energy density than the intensive homogenizer;

adding larger sized particles to a second mixer;

producing a second mixture by mixing the first mixture and the larger sized particles in the second mixer to substantially match the substantially fully homogenized conditions of the substantially second mixture without separating the multi-component macroscopic cement, the water, and the larger sized particles;

directing the second mixture into a third mixer having a lower energy density than the second mixer;

adding larger aggregate to the third mixer;

preparing a third mixture by mixing the second mixture and the larger aggregate in the third mixer to substantially match the substantially fully homogenized conditions of the third mixture without separating the multi-component macroscopic cement, water, larger sized particles, and larger aggregate.

86. The method of claim 85, wherein the multi-component macro-cement is a powdered macro-cement.

87. The method of claim 85, wherein the multi-component macroscopic cement is an engineered form of a macroscopic cement.

88. The method of claims 85 to 87, wherein reinforcing fibers are also added to the third mixer, and the third mixer is operated to substantially match the substantially fully homogenized conditions of the second mixture without separating multi-component macroscopic cement, water, larger sized particles, larger aggregates, and reinforcing fibers.

89. The method of claims 85-87 wherein the first mixture comprises a cementitious slurry and is passed through a shear rate γ_{Macroscopic cement}Is carried out with a plastic viscosity mu_{Macroscopic cement}The shear rate γ_{Macroscopic cement}Shear stress tau provided in cement slurries_{Macroscopic cement}At a dynamic yield stress tau corresponding to the minimum shear stress_{0 macroscopic cement}To the limit dynamic stress tau that keeps the slurry flowing to the structure corresponding to the complete destruction of the cement slurry_{d macroscopic cement}In which the ultimate dynamic stress τ_dAbout dynamic yield stress tau_{0 macroscopic cement}Ten times of so that_{0 macroscopic cement}＜τ＜10τ_{0 macroscopic cement}。

90. The method of claim 89, wherein said ultimate dynamic stress τ_dAbout dynamic yield stress tau_{0 macroscopic cement}Quadruple of so that_{0 macroscopic cement}＜τ＜4τ_{0 macroscopic cement}。

91. The method of claim 89, wherein the plastic viscosity μ_{Macroscopic cement}From about 0.01 to about 1Pa^.s, the dynamic yield stress τ_{0 macroscopic cement}From about 10 to about 100Pa.

92. The method of claims 85-87, whereinThe second mixture comprises a mortar slurry and is passed through a shear rate γ_MortarIs carried out with a plastic viscosity mu_MortarThe shear rate γ_MortarShear stress tau provided in mortar slurries_MortarAt a dynamic yield stress tau corresponding to the minimum shear stress_{0 mortar}To the limit dynamic stress tau that keeps the slurry flowing to the structure corresponding to the complete destruction of the mortar slurry_{d mortar}In the range of (1), wherein the ultimate dynamic stress τ_{d mortar}About dynamic yield stress tau_{0 mortar}Ten times of so that_{0 mortar}＜τ＜10τ_{0 mortar}。

93. The method of claim 92, wherein the ultimate dynamic stress τ_{d mortar}About dynamic yield stress tau_{0 mortar}Quadruple of so that_{0 mortar}＜τ＜4τ_{0 mortar}。

94. The method of claim 92, wherein the plastic viscosity μ_MortarIs about 1 to about 10Pa^.s, dynamic yield stress τ_{0 mortar}From about 100 to about 500 Pa.

95. The method of claims 85-87, wherein the third mixture comprises a concrete slurry and is passed through a shear rate γ ™_{Concrete and its production method}Is carried out with a plastic viscosity mu_{Concrete and its production method}The shear rate γ_{Concrete and its production method}Shear stress tau provided in concrete slurry_{Concrete and its production method}At a dynamic yield stress tau corresponding to the minimum shear stress_{0 concrete}To the limit dynamic stress tau that keeps the slurry flowing to the structure corresponding to the concrete slurry completely destroyed_{d concrete}In the range of (1), wherein the ultimate dynamic stress τ_{d concrete}About dynamic yield stress tau_{0 concrete}Ten times of so that_{0 concrete}＜τ＜10τ_{0 concrete}。

96. The method of claim 95, wherein the ultimate dynamic stress τ_{d concrete}About dynamic yield stress tau_{0 concrete}Quadruple of so that_{0 concrete}＜τ＜4τ_{0 concrete}。

97. The method of claims 85-87, wherein the plastic viscosity μ_{Concrete and its production method}From about 10 to about 100Pa^.s, the yield stress τ_{0 concrete}From about 500 to about 2000 Pa.

98. The method of claims 85 to 87, wherein the strongly moving energized water stream is provided with input energy by any one of high pressure nozzles, rotor-stator mixers, venturi systems or ultrasonic processors, which is converted into friction, turbulence, micro-turbulence, waves, microwaves and cavitation to promote uniform and substantially complete macro-cement homogenization.

99. The method of claims 85-87, wherein the intensive homogenizer is a concrete mixer.

Technical Field

The present invention relates to a macroscopic cement, and more particularly, to a method of producing a macroscopic cement from a micro-sized cementitious material with or without pozzolan particles coated with sub-micron or nano-scale particles or a combination thereof.

Background

The most widely used building materials in the world are partly or wholly made of cementitious materials, in particular concrete. Concrete generally refers to a mixture of natural and/or artificial aggregates, such as sand and gravel or crushed stone, held together by a binder of a cement slurry to form a highly durable building material. The slurry is typically composed of hydraulic cement (e.g. portland cement) and water, and may also contain one or more chemical admixtures, as well as supplementary cementitious materials such as fly ash, ground blast furnace slag and silica fume.

In the late 1970 s, Ultra High Performance Concrete (UHPC) was seen as a breakthrough in the materials industry, with increased compressive strength and higher durability exceeding 120MPa, compared to other high performance concretes known at the time. UHPC is also known as Reactive Powder Concrete (RPC) or densely packed cementitious material, often also called dense systems, which contain a uniform arrangement of ultra-fine particles (DSP material). Regardless of variations in the names of such concretes and compositions thereof, these cements are formed by hydrating densely packed particles of an inorganic binder with ultrafine particles of a less or non-reactive second filler, and some other particulate material. Those skilled in the art will appreciate that DSP materials produce mechanical qualities, including strength, density and durability, heretofore unattainable (examples include EP 0010777B 2, EP 0269715B 1, EP 0042935B 2, US4,979,992).

Inorganic binders are materials produced by mechanical comminution of coarser intermediates such as clinker and granulated blast furnace slag and typically comprise particles of between 1 μm and 100 μm in size. Even when such particles are piled to the theoretical maximum, there are still voids that cannot be filled with inorganic binder particles of this size range. The most common binder used in the production of UHPC is portland cement. After mixing with water, the voids between the inorganic binders are filled with liquid. However, it is known in the art that when the voids between the inorganic binders are filled with a second material having a smaller particle size than the inorganic binders, the amount of water is reduced. For example, US 5,522,926 discloses the use of silicon powder, particularly microsilica, which is the most commonly used ultra-fine material for filling the voids between inorganic binders. Such cement systems with two particle sizes exhibit higher degree of stacking, lower porosity, higher strength and lower permeability than conventional concrete.

Optimization of the granular blend and optimal use of superplasticizers for effective micro-and recently nano-reinforcement to enhance the compacted density are the most important factors defining the strength and processability of UHPC. The uniform distribution of cement-silica fume particles is critical to producing dense, strong concrete matrices. Based on the principle of optimizing mortar composition, concrete with significant compressive strength and fracture energy was designed with the goal of maximizing the matrix density of the concrete (US 5,522,926; US6,080,234; US7,901,504; US8,303,708). In addition, others have focused on maximizing mortar packing density (U.S. Pat. Nos. 7,744,690 and 8,016,938).

In view of the critical importance of increasing particle packing for making strong Concrete, a number of mathematical models have been developed, such as Shakhmenko et al Concrete Mix Design and Optimization,2^ndPhD Symposium in Civil Engineering 1998Budapest,1-8 and Yu et al Mix design and property of Ultra-High Performance Fibre Reinforced Concrete (UHPFRC), centre and Concrete Research 56(2014)29-39 for calculating the Concrete composition with the maximum particle packing density, and a number of software programs based on these mathematical models have been created to calculate this optimum composition.

The mathematical model that attempts to calculate an ideal concrete composition with maximum particle bulk density is based on the theory that a powder is "ideal", meaning that the powder is loose and has no interconnected agglomerated particles. According to this "ideal" powder theory, after mixing silica fume powder with a larger inorganic binder, the ultrafine silica particles are uniformly arranged in the interstices between the coarser cement particles, together forming a densely packed matrix. However, in actual practice, the silicon powder particles have a tendency to agglomerate. The smaller the particle size, the more aggregation. In current systems, the ultrafine silicon powder material will agglomerate, while the nanoparticles will agglomerate severely. Both particle size ranges agglomerate to form densely packed agglomerates, which reduces the benefits associated with silicon powders having small particle sizes. The agglomeration of the particles prevents uniform distribution of the silica fume particles and compromises the density and other properties of the concrete matrix in various ways, including but not limited to resulting in higher porosity, lower strength and durability, and higher permeability. Although many modern multi-component particle packing models take into account the interactions between different components, the basic mathematical equations of almost all particle packing models are identical and based entirely on particle geometry. However, these models do not suggest a solution to the problem of particle agglomeration.

As an example, EP 0042935B 2 describes and therefore known in the art that if the silicon powder particles agglomerate, some dispersion, such as grinding, can be applied. Thus, there are two problems to be solved for silica fume to be used as an effective ultrafine material to be mixed with an inorganic binder such as portland cement. Firstly, the aggregates should be broken down and secondly, the silica powder should be distributed uniformly throughout the concrete.

To address the problem of silica fume particle agglomeration, many modern cement manufacturers have experimented with dry blending silica fume with cement using various mills and mixers. The experience of these manufacturers, as well as the extensive experimentation of the authors in mixing dry cementitious compositions on various types of intensive mixers, has shown that these mixers fail to sufficiently depolymerize the silica powder to provide the maximum fill density of a multi-component cementitious mixture. Decomposing silica fume with cement during the cement grinding process has proven to be beneficial. However, cement grinding is usually carried out in factories using clinker grinding processes that produce large quantities for commercial use. One disadvantage of dry mixing silica fume during cement manufacture is the lack of production flexibility. In particular, it is impractical to produce relatively small and different batches of mixed hydraulic cements according to the needs of different customers. Another disadvantage is that a limited amount of silica fume can be added to the cement during its manufacture. The amount of silicon powder added is generally between 3% and 10% by weight, and is almost certainly below the maximum 15% specified by many national standards (in particular, canadian national standard CAN/CSA 3000-13). The amount of silica fume is generally lower than its optimum (up to 25% in many UHPC compositions and higher in some cases) to produce a blended cement composition with maximum bulk density. Furthermore, grinding cannot be used for optimum filling of multicomponent mixtures which, in addition to silicon powder, also contain other supplementary cementitious materials, such as fly ash, slag, etc., and also non-cementitious fillers, such as quartz powder, sand, etc. The reason that grinding cannot be used for optimum filling of a multi-component cementitious mixture is that it is not believed that the optimum proportions of the components can be calculated from the original sizes of the components, since the different components are comminuted to varying and unpredictable degrees during grinding.

More recently, examples include: nano silicon dioxide, nano clay, nano TiO₂Nano Fe₂O₃Nanoscale additives to carbon nanotubes and fibers are used to produce cementitious materials. However, it is known in the art that powder cohesion increases with decreasing particle size, and thus, disaggregation of nanoparticles and their uniform distribution in a cementitious matrix is an even more challenging problem than is the case with ultrafine particles. The nanoscale additives may be provided in the form of a suspension, for example nanosilica, or in the form of a powder, for example nano-TiO₂Carbon nanotubes and nanofibers. In the case of powdered nanotubes, the nanotubes are dispersed prior to adding them to the cementitious mixture. The dispersion of the nanotubes is carried out by methods utilizing high dispersion energy, including ultracentrifugation and sonication (US 8,865,107; US 20090229494). The dispersed nanotubes according to US8,865,107 and US 20090229494 can then be mixed with a cementitious material using a standard mixer. However, this has a low scoreStandard energy-dissipating mixers do not provide a completely uniform distribution of nano-sized particles or fibers in a cementitious matrix.

The optimal use of superplasticizers and the optimization of the dry adhesive mixture are the most important factors defining the strength and processability of UHPC. Superplasticizers, also known as high range water reducers, are chemical mixtures that require well dispersed particle suspensions. The addition of superplasticizers to mortars or concretes reduces the water-cement ratio without affecting the workability of the mixture, thus improving the properties of both fresh mortar and hardened concrete. One effective method of using superplasticizers is the ultra-high strength high performance concrete provided by Taylor and Francis Group, LLC in 2013, PuXincheng, in which the superplasticizers are adsorbed onto the surface of cement particles, thereby avoiding adsorption of most superplasticizers by aggregates, thereby reducing the plasticizing effect. Furthermore, EP0010777 discloses the introduction of a superplasticizer in dry powder form into the dry mixture prior to the addition of water as a more efficient way to utilize the superplasticizer.

Many prior art references disclose methods for improving dispersion by incorporating superplasticizers into cement dry blends. For example, EP0696262 discloses a process for producing cement which comprises reacting a geopolymer or mineral mixture of Portland cement with a SiO-containing compound₂The microfiller (e.g. silica flour and/or melamine or naphthalene based powdery water reducing agent) is subjected to a mechanochemical treatment in a grinding apparatus. RU 2577340 discloses combining powdered superplasticizers with cement, and WO2009084984 and RU2371402 disclose mixing dry superplasticizers with cement. Furthermore, Sobolev et al, 11.7.2006, in the American Denver conference "nanotechnology of concrete: recent Developments and future prospects "conference sets" Nanomaterials and nanotechnologies for High-Performance Cement Composites "pages 91-118 (" Nanomaterials and Nano-engineering for High-Performance Composites, Proceedings of Access on "Nanotechnology of concentrate: Recent Developments and future Performance additives" November 7,2006, Denver, USA, pp.91-118) have been described by mutually mixing Cement and dry modifier in a High-energy millGrinding, combining the superplasticizer with the cement, the purpose of which is to attach the organic functional groups of the superplasticizer to the surface of the inorganic Portland cement and to form an organomineral nanolayer on the surface of the cement. In particular, WO2014148944 creates the term "nanocement" to refer to the formation of a nanolayer of molten dry superplasticizer having a thickness of 20 to 100nm around cement particles.

All of the above-mentioned references are directed to superplasticizers being melamine or naphthalene; the superplasticizer substance is in a solid or powder state; the apparatus is a mill, in particular a ball mill; while the treatment stage is directed to cement grinding. These limitations lead to a number of disadvantages. First, melamine or naphthalene superplasticizers have been commonly replaced by polycarboxylate type water reducers. This problem is further exacerbated by the requirement to pulverize most of the superplasticizers on the market, which are liquids. Another disadvantage of adding melamine or naphthalene based superplasticisers directly on cement particles is that the observed chemical action interferes with the action of the superplasticisers. In particular, in the early stages of hydration of the spent water reducing agent, organic mineral phases may form around the cement particles in a non-productive manner. It is known in the art that a portion of the added superplasticizer can be inserted into different hydration products and this fraction is no longer available for dispersing Cement aggregates (Flatt, R.J., Houst, Y.F., amplified view on chemical effects in the action of superplastic, calibration and Concrete Research 31(2001) 1169-. However, there is also a problem in that the method of using superplasticizers in cement production processes is limited to using only one chemical additive (i.e. a polymeric water reducing agent) and not other chemical additives (e.g. hydration stabilizers), accelerators and other products in liquid form.

US 5,709,743 and US7,041,167 utilize ground calcium silicate hydrate (C-S-H) as a setting and hardening accelerator and strength enhancing additive for cementitious products. Recent studies in Land G and Stephan D (nanoparticies acquisition reactors for determination, Ultra-High Performance converter and Nuclear technology in Construction, Proceedings of High, Kassel, March 7-9,2012, pp.112-118)The kinetics of the nanoparticles on cement hydration and their potential to replace conventional setting and hardening accelerators are revealed, as well as their adverse side effects. It is taught that the addition of nanoparticles and most importantly nano C-S-H seeds to fresh cement slurries stimulates the nucleation process during early cement hydration, accelerates setting and hardening, and results in enhanced mechanical properties of the hardened cement slurry. However, submicron (especially nanoscale) C-S-H seeds are expensive to manufacture and involve complicated processing procedures, resulting in such accelerated curing admixtures for concrete (e.g., BASF)^TMMaster X-Seed produced^TM100) And are very expensive compared to known accelerating additives. Another disadvantage of using C-S-H as a promoter is that it must be added as an aqueous slurry. This is disadvantageous for UHPC blends because the addition of water contained in the C-S-H slurry affects the desired low water-to-gum ratio. Recent studies by Moghaddam, Sakineh E. et al, have proposed a method of synthesizing C-S-H under small-scale laboratory conditions, rather than on pilot or production scale, by an in situ generated Seed-mediated growth method, which is comparable to Master X-Seed^TM100 are much more expensive and are currently in the early stages of research (Moghaddam, Sakineh E., VahidHejazi, Sung Hoon Hwang, SreepraadSreenivasan, Joseph Miller, Benhang Shi, Shuo Zhao et al, "Morphogenesis of science hydrate," Journal of materials Chemistry A (2017). Doi:10.1039/C6TA 09389B).

Given the diversity of known mortar and concrete compositions and methods of making them, the methods of making shaped concrete elements and structures from these compositions can be roughly described by the basic method with slight variations in casting the dry cement composition with sand, aggregate, water and chemical additives, shaped elements and structures and hardening the object. The workability of the slurry and fresh concrete, as well as the quality of the hardened cementitious material, depends on the quality of the mixing process, and more specifically on how well the mixing process can provide a uniform distribution of the mixture ingredients and delivery of water and chemicals to each cement particle. In particular, it is known in the art that a mixture property is a certain amount of homogeneity and is therefore a "quality standard". In fact, in Dehn, F. in "Effect of Mixing Technology on Fresh Concrete Performance of HPFRCC", the symposium on the use of HPFRCC in structural applications by International RILEM, fire in USA, published by RILEM SARL in 2006 (knowledge of Mixing Technology on Fresh Concrete Properties of HPFRCC, Proceedings of Int' l RILEM works shop on HPFRCC in structural applications in Honolulu, USA, published by RILEM SARL,2006), teaches that in the Fresh state the Mixing process has a significant effect on the achievable Concrete Performance, while the efficiency of the mixer depends on the homogeneity of the produced Concrete.

The processing of cement slurries in various types of mixers, including drum mixers, disc mixers, gypsum/mortar mixers, planetary mixers and powerful airy mixers, has been extensively studied to investigate the workability of the slurry and various properties of the hardened concrete, such as, for example, density, strength, homogeneity of the various components in the concrete, cement hydration kinetics, and the like. It is known in the art to improve the properties of concrete by increasing the strength of the mixing process. However, such prior art mixing techniques have inherent limitations. In particular, existing mixing techniques do not achieve the highest possible strength of the hardened cementitious material. The increase in strength in the prior art mixing techniques can increase the homogeneity of the components and deliver water and chemical additives to the components to a finite mixing strength, after which further increases in mixing strength can lead to separation and component separation, which in turn leads to a degree of separation that reduces the strength of the concrete.

The mixture of cementitious materials is heterogeneous, containing different materials with a wide range of particle sizes, densities, shapes, etc. Consider a continuous body of cementitious material comprising three main product groups: cement slurries (cement-water system), mortars (cement-water-sand system) and concretes (cement-water-sand-aggregate system), it may be noted that the rheological characteristics of these groups differ significantly. Thus, each of these material groups requires its optimal energy to provide optimal homogenization. Existing mixing techniques typically deliver the same energy to all of the different assemblies and therefore, regardless of the mixer type, do not provide a particular set of assemblies with a particular desired energy and therefore do not provide optimal mixture homogenization. Another disadvantage of the existing mortar/concrete mixing techniques is the common work flow, i.e. adding water to the dry mix, which results in liquid-rich lumps or agglomerates when the water contacts the powder, followed by a large (sometimes additional) high-strength mechanical treatment. To homogenize the agglomerates and deliver water to most cement particles, water addition is required. Finally, the problems of the existing mortar/concrete process mixing techniques are magnified by the fact that: although the mixer designer appears to recognize that there may be significant differences in rheology between cement, mortar and concrete mixtures, there is no clear mathematical model to determine the rheology of each mixture and define the optimum mixing parameters based on such a model.

In addition to the problems associated with wet mixtures, problems associated with dry cement mixtures comprising portland cement and other fine and highly hygroscopic components such as silica fume are also recognized. These problems include, but are not limited to: reduced and limited shelf life, possibly harmful excess dust and separation of components during transport and handling of the mixture. An important property of cement is shelf life, which depends on its ability to retain its chemical activity during long term storage. Cement is a hygroscopic material and hydrates in the presence of moisture. The absorption of moisture in the air can result in irreversible chemical interaction of the cement with water. As a result, the cement loses activity in storage under the influence of moisture and carbon dioxide present in the atmosphere.

Portland cement is designed to chemically react with water and exposure to ambient moisture will cause it to set and harden. Depending on the storage conditions of the cement, its activity may be lost by about 15% per month. It is generally accepted that cement inevitably deteriorates during transport and storage, which means that its limited guaranteed shelf life is usually not more than 6 months, and in many cases, cement can be used for only 3 months or less after delivery. Dry cement mixes containing other highly hygroscopic materials (e.g. silica fume) in addition to silicate cement, including the known dry mix of UHPC, present even more problems with respect to limited shelf life. Thus, prior storage proposals for portland cement and dry mixes thereof suggest dehumidifying storage compartments with minimal airflow through the use of air-tight multi-layer plastic bags, and isolating the cement from the surrounding atmosphere by stacking it on walls.

Many prior art references have attempted to improve the shelf life of cement by utilizing alternative packaging techniques. For example, CN101428992A and CN102485687A describe dry mortar and two-component packaged cement packaged in a combined manner, wherein mortar components having different shelf lives are packaged separately, so that the shortest shelf life component (usually portland cement) does not negatively affect the shelf life of the whole mixture. This solution allows to maintain the activity of certain cement components, such as sand, until the mixing does not deteriorate, but these solutions do not allow to extend the shelf life of the cement. Once the components are mixed, the shelf life of the cement mixture is limited by the component with the shortest shelf life. CN 103420648A teaches a method for delaying cement setting and extending the useful life, wherein cement and dry sand are uniformly mixed in a weight ratio of 1 to 4, and the mixture is then packaged into two layers. This method requires that a portion of the ambient moisture be absorbed by the dry sand, thereby protecting the cement from premature hydration. However, the fact that cement is more hygroscopic than sand makes this method ineffective and not universally applicable to various mixtures of cement and sand. Furthermore, UHPC mix designs do not use this cement to sand ratio.

Other prior art references have attempted to improve the shelf life of cement by granulation. For example, US2,221,175 describes the granulation of portland cement to modify the cement for storage purposes and to eliminate dust nuisance by using water soluble binders or/and water insoluble binders. There are several problems with this granulation process. For water-insoluble binders, the particles/pellets should be reground to the original cement particle size before mixing with water, since the cement should be in a fine powder state when mixed with water in order to act as a hydraulic binder. Furthermore, the hardened water-insoluble binder will reduce the activity of the cement by covering a portion of the cement particles and creating a barrier to the manufacture of a hardened monolithic smooth cement matrix. In the case of water-soluble binders, the water in the binder will cause hydration of the cement and produce hydrated cement particles, which will reduce the activity of the cement and require regrinding of the cement containing hydrated aggregates. US8,992,679 describes dry construction pellets comprising uncured cement powder and a non-reactive binder, which may be a small amount of water, insufficient to fully cure the cement. However, pellets according to US8,992,679 have substantially the same problems as the above-mentioned US2,221,175. Furthermore, the small amounts of water described in US8,992,679 are not sufficient to fully set the cement. Instead, the disclosed amount of water will partially set the cement, thereby reducing the partial reactivity of the cement. Another disadvantage of dry granules according to US8,992,679 is that, despite the inclusion of cement, sand and gravel, the dry granules lack any necessary UHPC Supplementary Cementitious Material (SCM), such as silica fume, fly ash, etc. In addition, neither US2,221,175 nor US8,992,679 disclose that the cement comprises reinforcing microfibers.

It is known in the art that the efficiency of reinforcing fibers is defined by the strength of the fibers themselves and the strength of the bond between the fibers and the concrete matrix. Generally, smooth metal fibers have poor adhesion to cementitious matrices. There are two methods known in the art to improve this bond slip performance, one using fibers with certain special shapes (US4,960,649 and 5,981,630) and the other using chemical treatments to treat the fiber surface, such as: as strong acids, they can corrode the surface or be deposited on the fibers by mineral compounds (6,955,844; US6,478,867).

Finally, US4,031,184 relates to a method for recovering cement kiln dust, and US4,341,562 teaches kiln dust particles or cement kiln dust and fly ash pellets for the manufacture of lightweight concrete. These patents propose granulated cements for making non-soluble aggregates.

The following aims to obviate or mitigate at least one of the aforementioned disadvantages.

Disclosure of Invention

In one aspect, there is provided a multi-component macroscopic cement composition, comprising: a cementitious material comprising micron-sized particles; and a Supplementary Cementitious Material (SCM) of submicron or nanoscale particles or combinations thereof coated or supported on the cementitious material.

In embodiments, the cementitious material may further comprise micro-sized particles of a pozzolanic material.

In embodiments, the composition may further comprise aggregate.

In embodiments, the composition may further comprise reinforcing fibers.

In embodiments, the composition may further comprise a binder.

In embodiments, the composition may be produced in the form of granules, pellets, briquettes, or tablets.

In embodiments, the cementitious material may be portland cement, fly ash (class C as is), or slag (ground blast furnace dust).

In embodiments, the pozzolanic material may be fly ash (class F as such), coarse metakaolin, or calcined clay.

In embodiments, the SCM may be a silicon-SiO-containing₂The particles of (1).

In an embodiment, the siliceous-SiO-containing material₂The particles of (a) may be silica powder, quartz (fines), precipitated silica, fly ash (fines), metakaolin, or rice hull ash.

In embodiments, the SCM may be nanosilica, carbon nanotubes and nanofibers, nano-TiO₂Or nano Fe₂O₃A nanoclay.

In embodiments, the binder may be a polymer in the form of a liquid or powdered chemical additive.

In embodiments, the additives may be superplasticizers/high range water reducers, plasticizers/mid and normal range water reducers, and/or retarding or accelerating admixtures for concrete.

In embodiments, the SCM may be affixed to the cementitious material by dry coating without the use of an adhesive.

In embodiments, the aggregate may be a fine aggregate.

In embodiments, the fine aggregate may be natural or synthetic sand, quartz, or bauxite.

In embodiments, the composition may further comprise a coarse aggregate.

In embodiments, the coarse aggregate may be gravel, crushed stone, recycled concrete, or a geosynthetic aggregate.

In embodiments, the crushed stone may be limestone, basalt, granite, or bauxite.

In embodiments, the reinforcing fibers may be metal fibers, glass fibers, synthetic fibers, or natural fibers, including but not limited to cellulose and hemp fibers.

In embodiments, the metal fibers may comprise any one of steel, stainless steel, titanium, copper, or brass clad steel.

In embodiments, the synthetic fibers may include polypropylene, carbon fibers, or aramid fibers.

In an embodiment, during dry coating and/or loading of the macroscopic cement, the reinforcing fibers may be crushed by the aggregate to provide a scraping surface thereon, and wherein the scraping surface contains particles of the composition.

In embodiments, the composition may be produced in the form of granules, pellets, briquettes or tablets during the coating and/or loading of the cementitious material by mechanical activation.

In embodiments, the activation may include pressure and shear forces that cause the cementitious material to activate.

In another aspect, a method of producing a multi-component macroscopic cement is provided, the method comprising coating or supporting micro-sized particles of cementitious material with a Supplementary Cementitious Material (SCM) of sub-micron or nano-sized particles or a combination thereof.

In embodiments, the method may further comprise adding micro-sized particles of pozzolanic material to the cementitious material prior to the coating or loading.

In embodiments, the method may further comprise adding aggregate to the macroscopic cement prior to the coating or loading.

In embodiments, the method may further comprise adding reinforcing fibers to the macroscopic cement prior to the coating or loading.

In embodiments, the method may further comprise utilizing an adhesive.

In embodiments, the method may further comprise engineering the multi-component macroscopic cement by preparing the multi-component macroscopic cement as particles, pellets, briquettes, or pieces.

In embodiments, the cementitious material may be portland cement, having about 250m²/kg to about 750m²A fineness of blaine/kg, corresponding approximately to 10% of the diameter d₁₀0.7 μm to about 90% diameter d₉₀Particle size 70 μm.

In an embodiment, the portland cement may have a thickness of about 350m²/kg to about 550m²A fineness of blaine/kg, corresponding approximately to approximately d₁₀1 μm to about d₉₀Particle size 50 μm.

In embodiments, the cementitious material may be calcium aluminate cement.

In embodiments, the cementitious material may be fly ash (class C) having an approximate fineness of about 5% to 45% retained on 45 μm rejects, corresponding about to about d₁₀1 μm to about d₉₀Particle size 50 μm.

In embodiments, the cementitious material may be slag (ground blast furnace dust) having about 250m²Kg to about 600m²A fineness of blaine/kg, corresponding approximately to 10% of the diameter d₁₀1 μm to about 90% diameter d₉₀Particle size 70 μm.

In embodiments, the pozzolanic material may be fly ash (class F) having an approximate fineness of about 5% to 45% retained on a 45 μm rejects, corresponding about to about d₁₀1 μm to about d₉₀＝5Siliceous particles of particle size 0 μm.

In embodiments, the SCM of the submicron particle may be 5000m²Kg to 200000m²Silicon powder (microsilica) with a specific surface area of/kg.

In an embodiment, the silicon powder more specifically has 15000m²/kg to 30000m²A specific surface area per kg, or typically about 10nm (nanometers) to 1 μm.

In embodiments, the SCM may be present in an amount of 5-50% by weight of the cementitious material.

In embodiments, the SCM may be present in an amount of 20-40% by weight of the cementitious material.

In embodiments, the SCM particles may range in size from 1 to 100 nm.

In embodiments, the SCM particles may include nano-silica, carbon nanotubes and fibers, nano-clays, nano-TiO₂Nano Fe₂O₃Or other nano-sized SCM particles.

In embodiments, the amount of nanosilica may be from 0.25 to 10% by weight of the macroscopic cement.

In embodiments, the amount of nanosilica may be from 1 to 5% by weight of the macroscopic cement.

In embodiments, the amount of nanosilica may be 2-3% by weight of the macroscopic cement.

In embodiments, the amount of carbon nanotubes and fibers may be 0.003-1% by weight of the macrocement.

In embodiments, the amount of carbon nanotubes and fibers may be 0.01 to 0.5% by weight of the macrocement.

In embodiments, the amount of carbon nanotubes and fibers may be 0.05 to 0.1% by weight of the macrocement.

In an embodiment, the nano-TiO₂The amount of (b) may be from 0.01 to 10% by weight of the macroscopic cement.

In an embodiment, the nano-TiO₂May be in an amount based on the weight of the macroscopic cement1-5％。

In an embodiment, the nano-Fe₂O₃The amount of (b) may be from 0.01 to 10% by weight of the macroscopic cement.

In an embodiment, the nano-Fe₂O₃The amount of (b) may be 3-5% by weight of the macroscopic cement.

In embodiments, the binder may be a polymer in the form of a liquid or powdered chemical additive.

In embodiments, the binder may be a polymer in the form of a liquid chemical admixture for concrete.

In embodiments, the polymer may include water reducing, set retarding, binding, and other additives for concrete.

In embodiments, the water-reducing polymer may be a superplasticizer.

In embodiments, the superplasticizer may be a melamine or naphthalene or polycarboxylate.

In embodiments, the amount of the superplasticizer may be from 0.1 to 10% by weight of the macroscopic cement.

In embodiments, the amount of the superplasticizer may be from 0.5 to 5% by weight of the macroscopic cement.

In embodiments, the amount of the superplasticizer may be from 1 to 2.5% by weight of the macroscopic cement.

In embodiments, the retarding admixture may comprise any one of the following: lignin, borax, sugar, organic phosphate, tartaric acid and salts, sodium gluconate and sodium glucoheptonate, sodium phosphate and zinc salts.

In embodiments, the retarding admixture may be present in an amount of from 0.05 to 0.5% by weight of the macroscopic cement.

In embodiments, the bonding admixture may comprise any one of polyvinyl chloride, polyvinyl acetate, acrylic, and butadiene-styrene copolymer.

In embodiments, the coating may be performed by adhesive-free dry coating under conditions of strong mechanical force.

In an embodiment, the loading may be performed by dry coating with an adhesive under conditions of strong mechanical force.

In embodiments, the strong mechanical forces may include impacts, compressions and shear forces exerted on the particles, resulting in collisions of the particles with each other and repeated compression/shear deformation of the continuum of particles.

In embodiments, the aggregate may be a fine aggregate.

In embodiments, the fine aggregate may be natural or synthetic quartz or bauxite sand.

In embodiments, the method may further comprise coarse aggregate.

In embodiments, the coarse aggregate may be gravel, crushed stone, recycled concrete, or a geosynthetic aggregate.

In embodiments, the crushed stone may be limestone, basalt, granite, or bauxite.

In embodiments, the reinforcing fibers may be metal fibers, glass fibers, synthetic fibers, or natural fibers, including but not limited to cellulose and hemp fibers.

In embodiments, the metal fibers may comprise any one of steel, stainless steel, titanium, copper, or brass clad steel.

In embodiments, the synthetic fibers may include polypropylene, carbon fibers, or aramid fibers.

In an embodiment, during dry coating and/or loading of the macroscopic cement, the reinforcing fibers may be crushed by the aggregate to provide a scraping surface thereon, and wherein the scraping surface contains particles of the composition.

In embodiments, the macroscopic cement may be produced in the form of particles, pellets, agglomerates or sheets by mechanical activation during the coating and/or loading of the cementitious material.

In embodiments, the activation may include pressure and shear forces that cause physicochemical activation of the cementitious material.

In an embodiment, the particles may be produced directly during the coating and/or loading of the cementitious material into the apparatus performing the coating and/or loading process, the particles having a somewhat rounded or somewhat rounded and flattened shape and an equivalent spherical diameter of about 1 to about 20 mm.

In embodiments, after the coating and/or loading process of the cementitious material, the granules may be produced in a tumbling drum and pan, fluidized bed and mixing granulator, the granules having a somewhat rounded or somewhat rounded and flattened shape and an equivalent spherical diameter of about 1 to about 5 mm.

In embodiments, after the coating and/or loading process of the cementitious material, the granules may be produced in a tumbling drum and pan, fluidized bed and mixing granulator, the granules having a somewhat rounded or somewhat rounded and flattened shape and an equivalent spherical diameter of about 2 to about 10 mm.

In embodiments, the pellets may be produced by extrusion in an extruder or pelletizer after the coating and/or loading process of the cementitious material, the pellets having a cylindrical shape and an equivalent spherical diameter of about 5 to about 40 mm.

In an embodiment, after the coating and/or loading process of the cementitious material, the mass or sheet may be produced by compression at a roller having a shaped void, the mass or sheet having a slightly rounded or somewhat rectangular shape and an equivalent spherical diameter of about 10 to about 50 mm.

In embodiments, the agglomerates may be produced by compression from smooth rolls after the cementitious material coating and/or loading process, the agglomerates having an irregular fractured zone shape and an equivalent spherical diameter of about 3 to about 30 mm.

In yet another aspect, a method of producing a cementitious material using multi-stage homogenization is provided, the method comprising: producing a multi-component macroscopic cement by coating or supporting micro-sized particles of a cementitious material with sub-micron or nano-sized particles or a combination thereof of a Supplementary Cementitious Material (SCM); injecting the macroscopic cement into a strongly moving energized water stream; producing a first mixture by homogenizing a water stream with a macroscopic cement in an intensive homogenizer, the energy density of which is sufficient to overcome the cohesion of the macroscopic cement, to substantially completely disperse and homogenize without separating the multi-component macroscopic cement and water; directing the first mixture into a second mixer having a lower energy density than the intensive homogenizer; adding larger sized particles to a second mixer; producing a second mixture by mixing the first mixture and the larger sized particles in the second mixer to substantially match the substantially fully homogenized conditions of the substantially second mixture without separating the multi-component macroscopic cement, the water, and the larger sized particles; directing the second mixture into a third mixer having a lower energy density than the second mixer; adding larger aggregate to the third mixer; preparing a third mixture by mixing the second mixture and the larger aggregate in the third mixer to substantially match the substantially fully homogenized conditions of the third mixture without separating the multi-component macroscopic cement, water, larger sized particles, and larger aggregate.

In an embodiment, the multi-component macro-cement may be a powdered macro-cement.

In embodiments, the multi-component macroscopic cement may be an engineered form of the macroscopic cement.

In an embodiment, reinforcing fibers may also be added to the third mixer, and the third mixer is operated to substantially match the substantially fully homogenized conditions of the second mixture without separating the multi-component macroscopic cement, water, larger sized particles, larger aggregates, and reinforcing fibers.

In embodiments, the first mixture may comprise a cementitious slurry and pass through shear rate γ_{Macroscopic cement}Is carried out with a plastic viscosity mu_{Macroscopic cement}The shear rate γ_{Macroscopic cement}Shear stress tau provided in cement slurries_{Macroscopic cement}At a dynamic yield stress tau corresponding to the minimum shear stress_{0 macroscopic cement}To keep the slurry flowing to the opposite of the structure where the cement slurry is completely destroyedUltimate dynamic stress tau_{d macroscopic cement}In which the ultimate dynamic stress τ_dAbout dynamic yield stress tau_{0 macroscopic cement}Ten times of so that_{0 macroscopic cement}＜τ＜10τ_{0 macroscopic cement}。

In an embodiment, the ultimate dynamic stress τ_dMay be about dynamic yield stress τ_{0 macroscopic cement}Quadruple of so that_{0 macroscopic cement}＜τ＜4τ_{0 macroscopic cement}。

In an embodiment, the plastic viscosity μ_{Macroscopic cement}Can be from about 0.01 to about 1Pa.s, the dynamic yield stress τ_{0 macroscopic cement}And may be from about 10 to about 100Pa.

In embodiments, the second mixture may comprise a mortar slurry and is passed through a shear rate γ_MortarIs carried out with a plastic viscosity mu_MortarThe shear rate γ_MortarShear stress tau provided in mortar slurries_MortarAt a dynamic yield stress tau corresponding to the minimum shear stress_{0 mortar}To the limit dynamic stress tau that keeps the slurry flowing to the structure corresponding to the complete destruction of the mortar slurry_{d mortar}In the range of (1), wherein the ultimate dynamic stress τ_{d mortar}About dynamic yield stress tau_{0 mortar}Ten times of so that_{0 mortar}＜τ＜10τ_{0 mortar}。

In an embodiment, the ultimate dynamic stress τ_{d mortar}May be about dynamic yield stress τ_{0 mortar}Quadruple of so that_{0 mortar}＜τ＜4τ_{0 mortar}。

In an embodiment, the plastic viscosity μ_MortarCan be from about 1 to about 10Pa.s, dynamic yield stress τ_{0 mortar}And may be from about 100 to about 500 Pa.

In embodiments, the third mixture may comprise a concrete slurry and is passed through a shear rate γ_{Concrete and its production method}Is carried out with a plastic viscosity mu_{Concrete and its production method}The shear rate γ_{Concrete and its production method}Providing in concrete slurryShear stress τ of_{Concrete and its production method}At a dynamic yield stress tau corresponding to the minimum shear stress_{0 concrete}To the limit dynamic stress tau that keeps the slurry flowing to the structure corresponding to the concrete slurry completely destroyed_{d concrete}In the range of (1), wherein the ultimate dynamic stress τ_{d concrete}About dynamic yield stress tau_{0 concrete}Ten times of so that_{0 concrete}＜τ＜10τ_{0 concrete}。

In an embodiment, the ultimate dynamic stress τ_{d concrete}May be about dynamic yield stress τ_{0 concrete}Quadruple of so that_{0 concrete}＜τ＜4τ_{0 concrete}。

In an embodiment, the plastic viscosity μ_{Concrete and its production method}Can be from about 10 to about 100Pa.s, the yield stress τ_{0 concrete}And may be from about 500 to about 2000 Pa.

In an embodiment, the strongly moving energized water stream may be provided with input energy by any of a high pressure nozzle, a rotor-stator mixer, a venturi system, or an ultrasonic processor, which is converted to friction, turbulence, micro-turbulence, waves, microwaves, and cavitation to promote uniform and substantially complete macro-cement homogenization.

In an embodiment, the intensive homogenizer may be a concrete mixer.

Drawings

The above and other features, aspects, and advantages of the present invention will be described in detail below with reference to the accompanying drawings of various embodiments, which are intended to illustrate and not to limit the present invention. Embodiments will be better understood with reference to the accompanying drawings, in which:

fig. 1 is a flow diagram of a method of producing macroscopic cement according to one embodiment.

Figure 2 shows a diagram of suspended cement particles.

FIG. 3 illustrates the use of submicron SiO₂Graph of suspended cement particles dry coated with particles and nano-sized particles.

FIG. 4 illustrates a composite film formed from a composition comprising submicron SiO₂And/or nano-sized particle coated micro-sized carrier cementitious material or pozzolan particles.

Figure 5 shows a Scanning Electron Microscope (SEM) image of pozzolan fly ash particles dry coated with silica powder without binder x 25000 times.

FIG. 6 shows a coating containing submicron SiO₂And nano-sized particles and bound by chemical additives.

FIG. 7 shows a submicron SiO₂A map of coated micro-sized cementitious or pozzolan carrier particles and nano-sized supported particles bound by chemical additives.

Fig. 8 shows a Scanning Electron Microscope (SEM) image, magnified x 25000 times, of cement particles coated with silica fume and bonded by a chemical additive-superplasticizer binder.

Fig. 9 shows a Scanning Electron Microscope (SEM) image with magnification of 500000 cement particles coated with silica powder and added with chemical additive-superplasticizer as binder, and a clear view of the superplasticizer column (oblong rope in the center of the picture) to bind the silica powder particles to each other and to the cement particles.

Fig. 10 shows a cross-sectional view of macroscopic cement particles agglomerated (granulated) by tumbling.

Figure 11 shows a cross-sectional view of macroscopic cement particles agglomerated (granulated) by extrusion.

Figure 12 shows a method of engineering macroscopic cements by tumbling granulation and by tumbling granulation (agglomeration).

Fig. 13 illustrates a method of macro-cement granulation by compaction by extrusion and engineered macro-cement granules.

Figure 14 illustrates a method of macroscopic cementitious compact by compaction by a roller having surface agglomerate-like voids and engineered macroscopic cementitious agglomerates.

Figure 15 shows a method of consolidating a macroscopic cement compact by compression with smooth rollers and an engineered macroscopic cement parison (fractured zone containing reinforcing steel microfibers).

Fig. 16 shows a flow diagram of a method of making a shaped element or structure from macroscopic cement having a series of wet processing steps.

Figure 17 shows a cross-sectional view of a densely packed hardened macroscopic cement object.

FIG. 18 shows a Bingham model plot as a function of yield stress τ₀Shear rate γ and plastic viscosity μ characterize the rheology of the cement.

Figure 19 shows a rheological curve describing the effect of shear stress τ on the plastic viscosity μ of fresh cementitious material.

Figure 20 shows a rheological curve demonstrating the effect of shear stress τ on the plastic viscosity μ of some macroscopic cement slurries, mortars and concretes.

Figure 21 shows a table summarizing the range of rheological parameters for macroscopic cement slurries, mortars and concretes.

Figure 22 shows a rheological model illustrating the range of plastic viscosity/shear stress for macroscopic cement slurries, mortars and concretes.

Fig. 23 shows an exemplary orientation of a block for a thin slice.

Fig. 24 shows a thin layer transmitted light image of a hardened conventional mixture compared to a macroscopic cement mixture.

Fig. 25 shows the orientation of the samples for porosity analysis.

Fig. 26 shows a scanned image of a polished plate of hardened conventional mixture compared to a macroscopic cement mixture used to determine the hardened porosity parameter.

Fig. 27 shows a plot of the porosity intercept length distribution of a hardened conventional mixture compared to a hardened macrocement mixture.

Figure 28 illustrates various process flow options for producing macroscopic cement by dry coating and making concrete from the macroscopic cement using a multi-stage homogenization process.

Figure 29 illustrates various process flow options for producing macrocement by coating a micron-sized cement with or without pozzolan particles with submicron and nanoparticles in the presence of a chemical admixture and making concrete from the macrocement using a multistage homogenization process.

Figure 30 shows two process flow options for producing macro-cement by coating micro-scale cement with or without pozzolan particles with sub-micron and nano-particles in the presence of a chemical mixture, a chemical admixture, and also adding sand/aggregate/fiber and optionally engineered forms of macro-cement, and making concrete from the macro-cement using a multi-stage homogenization process.

Fig. 31 shows Scanning Electron Microscope (SEM) images at various magnifications of steel reinforcing fibers scratched and dented during the macro cement dry coating process.

Fig. 32 shows Scanning Electron Microscope (SEM) images at various magnifications of steel reinforcing fibers scratched and dented in a macroscopic cement loading process.

Detailed Description

For simplicity and clarity of illustration, where considered appropriate, reference numerals may be repeated among the figures to indicate corresponding or analogous elements. In addition, numerous specific details are set forth in order to provide a thorough understanding of the embodiments described herein. However, it will be understood by those of ordinary skill in the art that the embodiments described herein may be practiced without these specific details. In other instances, well-known methods, procedures, and components have not been described in detail so as not to obscure the embodiments described herein. Moreover, this description is not to be taken as limiting the scope of the embodiments described herein.

Unless the context indicates otherwise, various terms used throughout this specification may be read and understood as follows: as used throughout this document, "or" is inclusive as if written as "and/or"; the singular articles and pronouns used throughout this document include the plural forms thereof and vice versa; similarly, the gender pronoun includes its counterpart and should not be construed to limit any of the concepts described herein to a single gender use, implementation, presentation, etc. "exemplary" should be understood as "illustrative," "exemplary," or "serving as an example, instance, or illustration," and not necessarily "preferred" over other embodiments; the terms "comprising" and "including" are to be construed as inclusive and open-ended, rather than exclusive. In particular, the terms "comprises" and "comprising," and variations thereof, as used in this specification including the claims, are intended to imply the inclusion of a stated feature, step or component. These terms are not to be interpreted to exclude the presence of other features, steps or components; the terms "about" and "approximately" when used in conjunction with a range of particle sizes, composition of mixtures, or other physical properties or characteristics, are intended to encompass minor variations in the upper and lower limits of the ranges that may be present. Dimensions so as not to exclude embodiments where on average most of the dimensions are met but statistically dimensions may exist outside of this region. It is not intended that embodiments such as these be excluded from the present disclosure. Further definitions of terms may be set forth herein; however, it will not be described in detail hereinafter. As will be understood from reading this specification, these may apply to previous and subsequent examples of those terms.

The following relates to macroscopic cements and related methods for making pastes, mortars, concretes and other cementitious materials with high workability, high density and high strength. More specifically, the following relates to a process for the manufacture of macroscopic cements comprising cement, Supplementary Cementitious Materials (SCM) comprising siliceous submicron and nanoscale particles and a polymer in the form of a liquid or dry chemical admixture for concrete. The cement mixture can be used for preparing Ultra High Performance Concrete (UHPC).

The particles are fixed with chemical admixtures and/or by dry coating, homogenized in high-grade water, and mixed uniformly in water with sand and/or other aggregates of larger size at a lower grade level in a subsequent process step. The mixture may be cast into the shaped element and hardened. Optionally, after the particles are fixed with the chemical admixture or by dry coating, the macroscopic cement mixture can be processed into a solid form, such as particles, pellets, briquettes, or pieces. The process produces low or dust-free macroscopic and engineered cements, where the cement can be used to make Ultra High Performance Concrete (UHPC).

The term "macroscopic cement" refers herein to the mixture of dried macroscopic cement resulting from the combination of these ingredients and the ingredients themselves. In embodiments, the following provides a method of producing "engineered forms of macroscopic cements", such as granular, spherical, agglomerated, flake engineered, dust-free macroscopic cement forms, having extended shelf life and high workability, useful for making pastes, mortars, concretes, and other cementitious materials having high density and strength, increased early and final strength, and increased reaction rates of cement mixtures. Furthermore, a method is provided for homogenizing the macroscopic cement composition or engineered form of the macroscopic cement in water at various energy levels and adding sand and aggregate at a subsequent stage, and optionally setting an accelerating mixture that can be added to the sand and/or aggregate.

The following exemplary embodiments include a method of manufacturing a macroscopic cement and a multi-stage homogenization process for preparing a macroscopic cement-based material. The method may include mechanical processing of a micron-sized cementitious material, such as portland cement, fly ash (as-is-C) or slag (ground blast furnace dust) or pozzolan particles, such as fly ash (as-is-F), coarse metakaolin or calcined clay, etc., sub-micron SCM particles, such as silica fume, fly ash (fines), quartz (fines), precipitated silica, metakaolin, rice hull ash, etc., nano-scale SCM particles, such as nano-silica, carbon nanotubes and nanofibers, nano-TiO₂Nanoclays, etc., the binder is a polymer in the form of a liquid or powdered chemical additive, such as a superplasticizer/high range water reducer, and/or a plasticizer/mid and normal range water reducers and/or retarders, accelerators (such as set or early strength) or other chemical admixtures of concrete, the method comprising homogenizing a macroscopic cement composition in water at a high energy level to form a paste and in a subsequent process step, homogenizing the paste with larger size sand and/or aggregates at a lower energy level and casting the mixture into a shaped element and hardening.

Another exemplary embodiment below includes a method of making granulated, pelletized, agglomerated, or tabletted engineered macroscopic cements, wherein the large macroscopic cement is granulated, pelletized, agglomerated, or tabletted prior to wet homogenization.

Generally, the process of making macroscopic cements comprises a mechanical multistage process. In the first stage, the SiO-containing particles of submicron size can be first introduced₂The particles are coated onto larger micron-sized cementitious particles, with or without pozzolan particles (also referred to as "carriers"), and the nanoscale SCM particles can then be loaded onto the coated SiO-containing particles₂On a carrier for the particles. Alternatively, the larger micron-sized support may be first coated with the nano-sized SCM particles, followed by the sub-micron SiO-containing coating₂The particles of (a); then, the nanoparticles are coated on the carrier. Coating of only submicron-sized SiO-containing₂Or nano-sized SCM particles; or simultaneously coating submicron SiO-containing₂A mixture of particles and nano-sized SCM particles. In the second stage, the larger micron-sized cementitious materials (if present) and pozzolan particles may be coated with powdered or liquid chemical additives such as plasticizers, superplasticizers, set retarders or accelerators (set and/or early strength), or other chemical admixtures of concrete.

Another embodiment includes a composition comprising SiO₂The hygroscopic layer of (a) encapsulates or "coats" the cementitious or pozzolan carrier. Containing SiO₂The particles of (a) may also be coated or loaded with nanoscale materials, or simultaneously incorporated into a suspension of nanoscale particles in water or other liquid, or optionally into dried nanoparticles. The coated cementitious material or pozzolan carrier can be exposed to chemical additives such as plasticizers, superplasticizers, retarders, accelerators or other chemical admixtures for concrete. The liquid chemical admixture, in addition to serving as a modifier of the properties of the fresh and hardened concrete, also acts as a binder between the carrier and the coated particles and between the coated particles, fixing the coated particles to the carrier particles.

The amount of siliceous microfiller is calculated to produce the maximum packing density of pastes, mortars, concretes and other cementitious materials according to the following embodiment. To maximize the hardening properties of cement products, the nanoscale range was calculatedNumber of particles, e.g. nano-silica, carbon nanotubes and fibres, nano-clay, nano-TiO₂Or nano Fe₂O₃. The amount of liquid or dry chemical admixture is calculated to reliably immobilize SCM particles supported on a cement or pozzolan carrier and to provide high workability of these cementitious materials at low water content. Set accelerating and/or early strength accelerating additives such as, but not limited to, calcium chloride, triethanolamine, sodium thiocyanate, sodium formate/calcium, sodium nitrite/calcium, calcium nitrate, aluminates, and silicates may be used. The setting accelerating and/or early strength accelerating admixture may be dosed in an amount of from about 0.1% to about 20% by weight of the cementitious material, and in most applications, preferably from about 0.5% to about 10% by weight of the cementitious material.

Another embodiment below includes a method of producing engineered granulated, pelletized, agglomerated or tableted macroscopic cements. The cementitious or pozzolanic carrier is coated with SCM particles by dry coating, and optionally functional chemical additives are incorporated, and may also be loaded with SCM particles of the same size or small prior to engineering. Specifically, the liquid chemical admixture may be first deposited to contain SiO₂On the surface of the particles of (2), the SiO₂The particles form a hygroscopic microlayer encapsulating larger cement and pozzolan particles, or a liquid chemical admixture may be deposited onto the surface of the material in which the nanoparticles encapsulate the cement. Can be made of SiO-containing₂Is deposited to contain submicron-sized SiO-containing particles or liquid chemical mixtures₂And the nano-sized SCM particles. The shape, size and density of the engineered macrocement, the SCM particle coating amount and the amount of the liquid chemical admixture are determined in order to maximize the shelf life of the engineered macrocement and minimize dusting and separation of its powdered components.

Other embodiments below include homogenizing the macroscopic cement composition or engineered form of the macroscopic cement in water at various energy levels and adding sand and aggregate at a later stage, and optionally providing an acceleration admixture that can be loaded onto the sand and/or aggregate. The wet mixing procedure utilizes a multistage homogenization of macroscopic cement powder or macroscopic cement in engineered form, which differs at each stage of energy density, characterized in that in the first stage the macroscopic cement powder or macroscopic cement in engineered form is injected into a strongly moving stream of an electrically energized liquid and homogenized at the energy density required to overcome the cohesion of the macroscopic cement, so as to be substantially completely dispersed and homogenized without separation of the mixture components, the subsequent steps consisting in unloading the homogenized mixture from the homogenizer to a high energy density, then directing the mixture into a less dense mixer of lower energy density, and in each step adding larger sized particles (such as sand and aggregate) into the less dense mixer and mixing at a lower energy density matching the conditions of substantially complete homogenization of energy density, without the need to separate the mixture components.

For the purposes of the foregoing, certain aspects, advantages and novel features are described herein. It is to be understood that not necessarily all such advantages may be achieved in accordance with any particular embodiment described below. Thus, for example, those skilled in the art will recognize that the following may be embodied or carried out in a manner that achieves one advantage or group of advantages as taught herein without necessarily achieving other advantages as may be taught or suggested herein. While numerous changes may be made by those skilled in the art, such changes are within the spirit of the invention.

The methods of producing macro-cement and engineered forms of macro-cement described herein include a multi-stage process (fig. 1). The first stage of the process involves mechanical treatment of cement (shown as 200 in figure 2) with or without pozzolan particles (referred to as "carrier particles") with a Supplementary Cementitious Material (SCM) that may include micro-siliceous, sub-micron particles and/or nano-particles, with a single layer comprising SiO₂Are coated with cement particles (referred to as "loading particles"). Fig. 3 shows an example of several carrier particles (300) coated with a supporting particle (302). FIG. 4(a) shows a composite of submicron SiO containing particles (402)₂Coated micron-sized cementitious or pozzolan carrier particles (400). FIG. 4(b) showsMicro-sized cementitious or pozzolan carrier particles (400) coated with nano-sized particles (404). FIG. 4(c) shows a submicron SiO crystal composed of (402)₂And a mixture of nanoscale particles (404) coated micron-sized cementitious or pozzolan carrier particles (400). FIG. 4(d) shows submicron SiO containing particles (402)₂Which are coated with nanoscale particles (404) and then loaded together onto micron-sized cementitious or pozzolan carrier particles (400). FIG. 4(e) shows a reduced view from the sub-micron SiO contained (402) view relative to the other views in FIG. 4₂And nano-sized particle (404) coated micro-sized cementitious or pozzolan carrier particles (400). Figure 5 shows a Scanning Electron Microscope (SEM) image of pozzolan fly ash particles dry-coated with silica powder without binder, multiplied by 25,000.

The second stage comprises depositing a liquid chemical admixture or a dry coating on the SiO-containing layer₂On the surface of the loaded particles, a hygroscopic microlayer is formed that encapsulates the cement and pozzolan particles. For example, FIG. 6 shows a coating with submicron SiO₂And nano-sized particles and bound by chemical additives. FIG. 7 shows a submicron SiO₂A map of coated micron-sized cementitious or pozzolan carrier particles (700), the submicron SiO₂Comprising (702) and nanoscale-loaded particles (704) bound by a chemical additive (706). FIG. 7(a) shows a detailed view of micron-sized cementitious or pozzolan carrier particles (700) initially formed from submicron SiO comprising particles (702)₂Coated, then coated with nanoscale particles (704) and bound by chemical additives (706); FIG. 7(b) shows the coating first with nanoscale particles (704) and then with submicron SiO with particles (702)₂A detailed view of micron-sized cementitious or pozzolan carrier particles (700) coated and bound by chemical additives (706). FIG. 7(c) shows a composite film composed of submicron SiO containing (702)₂A detailed view of micro-sized cementitious or pozzolan carrier particles (700) coated with a mixture of nano-sized supported particles (704) and all bound by chemical additives (706); FIG. 7(d) shows submicron SiO containing particles (700)₂Is coated with nanoscale guest particles (704) and chemically addedThe agents (706) are combined and then loaded together onto micron sized cementitious or pozzolan host particles (702) and combined by chemical additives (706).

Specifically, the coated cement particles are mixed with a binder. The binder may be a polymer in the form of a liquid or powdered chemical additive (i.e. superplasticizer/high range water reducer, plasticizer/mid and normal range water reducer) and/or a retarder, accelerator or other chemical admixture for concrete, as well as a polymer in the form of a liquid chemical admixture for concrete. The liquid chemical admixture is deposited on a moisture-absorption layer formed by including micro-scale siliceous particles, sub-micron scale particles and/or nano-scale particles around cement particles (as shown in fig. 7). The SCM-coated particles are immobilized on a cementitious carrier with or without pozzolan particles using an adhesive, thus becoming a carrier coated with SCM particles and a polymer layer if cementitious and pozzolan particles are present. An example is shown in fig. 2. Fig. 8 is a Scanning Electron Microscope (SEM) image of cement particles at magnification x 25,000 times coated with silica powder and bonded by a chemical additive-superplasticizer. Fig. 9 shows a Scanning Electron Microscope (SEM) image, magnifying x 500000 cement particles coated with silica fume and added a chemical additive, superplasticizer, as a binder, and a clear view of the superplasticizer column (oblong rope in the center of the picture) bonding the silica fume particles to each other and to the cement particles.

A method of producing a macroscopic cement in engineered form comprising the steps of: granulation (shown in fig. 12 (a)), granulation (shown in fig. 13 (a)), agglomeration (shown in fig. 14 (a)), or tableting (shown in fig. 15 (a)). The method may further include homogenizing the macro-cement or engineered form of the macro-cement in water with other building aggregates such as sand and set accelerating additives, which may be coated onto the building aggregates for subsequent casting and hardening (fig. 16).

During the mixing of the macroscopic cement powder with water, a plurality of water molecules are wedged between the load particles and the carrier particles. The water weakens the binding force between the loaded particles. As a result, the particle-laden layer or layers become deformable. Specifically, as can be seen in fig. 17, during the treatment of mortar/concrete in the fresh state, the layer of loaded particles (1700) is plastically deformed and the particles are displaced to take a form suitable for the maximum packing density in the interstices between the cement and/or pozzolan particles (1702) of the entire mortar/concrete matrix. The matrix consists essentially of cement particles surrounded by fine silica particles and/or ultrafine nanoparticles that fill the voids between the larger cement or pozzolan carrier particles. In the case where the surfactant is a water reducing agent, deformation of the loaded particles is most pronounced.

As used herein, a cementitious or pozzolan micron-sized carrier can include, for example, cementitious materials such as portland cement, fly ash (class C as-is), slag (ground blast furnace dust), and pozzolans such as fly ash (class F as-is), coarse metakaolin, calcined clay, and the like, as well as any other cementitious or pozzolan micron-sized carrier. The term "portland cement" or "cement" as used herein generally includes the type of product obtained by heating a lime-clay mixture or natural cement-rock to a temperature at which the entire product is actually sintered and then ground. Various additives may be included in accordance with conventional portland cement production practices. It is to be understood that in the compositions and methods provided herein, various modifying agents, such as hydraulic cement, commonly referred to as calcium aluminate cement, can be used in place of portland cement, as an equivalent thereof. As an example of a cementitious carrier, a material having a thickness of about 250m may be used²/kg to about 750m²A fineness of blaine/kg, corresponding approximately to 10% of the diameter d₁₀0.7 μm to about 90% diameter d₉₀Cement particles with a particle size of 70 μm. More preferably, a coating having a thickness of about 350m may be used²/kg to about 550m²A fineness of blaine/kg, corresponding approximately to approximately d₁₀1 μm to about d₉₀Cement particles with a particle size of 50 μm. As an example of a quartz (finely ground) material, about d may be used₁₀1 μm to about d₉₀20 μm siliceous particles. More preferably, about d may be used₁₀2 μm to about d₉₀Siliceous particles of 10 μm. As an example of a fly ash F material, one can use at 45 μThe approximate fineness retained on the m screen residue is about 5% to 45%, corresponding about to about d₁₀1 μm to about d₉₀Pozzolanic siliceous particles of particle size 50 μm. As an example of a fly ash C material, an approximate fineness of about 5% to 45% retained on a 45 μm screen residue, corresponding about to about d, can be used₁₀1 μm to about d₉₀Cementitious particles with a particle size of 50 μm.

Sub-micron siliceous particles as used herein may include siliceous materials such as silica fume, fly ash (fines), quartz (fines), precipitated silica, metakaolin, rice hull ash, and the like, as well as any other sub-micron siliceous particles known in the art. As an example of submicron-sized siliceous particles, a specific surface area of 5000m can be used²Kg to 200000m²/kg, more particularly 15000m²/kg to 30000m²A silicon powder (microsilica) of/kg, or typically about 10nm (nanometers) to 1 μm. The amount of sub-micron siliceous material is calculated to produce the maximum packing density of the slurry, mortar, concrete and other cementitious materials. In particular, the amount of siliceous sub-micron particles is between 5 and 50% by weight of the cementitious or pozzolanic micron carrier (e.g., cement or fly ash), and for the density of the cementitious matrix it is more desirable to use between 20 and 40% by weight of the cementitious or pozzolanic micron carrier.

The nanoscale SCM particles may range in size from 1-100nm and may include nanosilica, carbon nanotubes and fibers, nanoclays, nano TiO₂Nano Fe₂O₃And any other nano-sized SCM particles known in the art. The amount of nano-sized SCM particles is calculated to maximize the performance of the hardened cement product and may vary greatly depending on the type of nanomaterial. Specifically, depending on the composition of the cementitious mixture, the amount of nanosilica may be from 0.25 to 10% by weight of the cement, and more preferably from 1 to 5% by weight of the cement, and even more preferably from 2 to 3% by weight of the cement. Depending on the composition of the cementitious mixture, the amount of carbon nanotubes and fibers can range from 0.003 to 1% by weight of the cement, and more preferably from 0.01 to 0.5% by weight of the cement, and even more preferablyMore preferably 0.05-0.1% by weight of cement. Depending on the composition of the cement mixture, nano TiO₂The amount may be from 0.01 to 10% by weight of the cement, and more preferably from 1 to 5% by weight of the cement. Depending on the composition of the cementitious mixture, nano-Fe₂O₃The amount may be from 0.1 to 10% by weight of the cement, and more preferably from 3 to 5% by weight of the cement.

Polymers used herein in the form of liquid chemical admixtures for concrete can include water reducing, retarding, binding and other admixtures for concrete. Specifically, any type of water reducing agent, including the following superplasticizers: melamine (sulfonated melamine formaldehyde), naphthalene (sulfonated naphthalene formaldehyde) and polycarboxylate mixtures; and the following common and intermediate plasticizers: lignosulphonate, hydroxycarboxylic acid salt, carbohydrate. The liquid chemical admixture, in addition to acting primarily as a modifier of the properties of the fresh and hardened concrete, also acts as a binder between the carrier and the loaded particles and between the loaded particles, fixing the loaded particles to the carrier particles. The cementitious mixture used herein may include any type, including: polyvinyl chloride, polyvinyl acetate, acrylic and butadiene-styrene copolymers.

The retarding mixture used herein may include any type, including: lignin, borax, sugar, organic phosphate, tartaric acid and salts, sodium gluconate and sodium glucoheptonate, sodium phosphate and zinc salts.

The amount of liquid chemical mixture is calculated in order to coat the SCM particles onto a cementitious or pozzolan micron-sized carrier, thereby providing high processability of these cementitious materials at low water content. In embodiments, the larger cementitious or pozzolan carrier particles are first mixed with the smaller submicron-sized load particles, and then a chemical admixture is applied to the mixture to bind all the particles together. Depending on the type of superplasticizer, the composition of the cementitious mixture and the designed water/binder ratio, the amount of superplasticizer is from 0.1 to 10% by weight of the dry matter of the superplasticizer, preferably from 0.5 to 5% by weight of the cement, even more preferably from 1 to 2.5% by weight of the cement, based on the weight of the cement. In these embodiments, depending on the type of admixture and the composition of the cementitious mixture, the amount of retarder is 0.05 to 0.5% by weight of retarder dry matter, and more preferably 0.1 to 0.3% by weight of cement, based on the weight of cement.

The method comprises coating cement with or without pozzolan particles by dry coating with small size silica fume particles by using high energy level mixing (figure 4) and optionally or alternatively mixing with particles with liquid chemical admixtures. For example, once cement and pozzolan particles are dry coated with small size silica fume particles at high energy levels, one option is to apply a liquid chemical admixture to the silica fume layer (fig. 7 a). Another option is to first mix the silica fume particles with a liquid chemical admixture and then apply the other admixture to the cement and pozzolan particles (if present). Alternatively, the silica fume particles are mixed with a portion of the liquid admixture, and the other admixture is applied to the cement and pozzolan particles, followed by the remainder of the admixture. In the case of both submicron and nanoscale siliceous particles, either particle size can be mixed with the cement and pozzolan particles, followed by application of the liquid chemical admixture, followed by addition of the other particle size, and optionally addition of further chemical admixture (FIGS. 7 c-e). Another option is to first mix the submicron and nanoscale siliceous particles, coat the submicron particles with nanoscale particles, and then add the chemical admixture in the presence of or prior to mixing the mixture of submicron and nanoscale siliceous particles with the cement and pozzolan particles (fig. 7 d).

Depending on the relative amount of carrier to loaded particles and their associated properties, the choice of equipment and operating conditions results in discrete particles, a continuous monolayer of particles, or multiple layers (stacks) of particles loaded onto carrier particles. In particular, the first step of coating or dry coating larger carrier particles with smaller SCM particles is performed under conditions of strong mechanical forces (e.g., impact, compressive and shear forces exerted on the particles), resulting in repeated compression/shear deformation of the particles from a continuum of particles. Machines which can be used for this purpose are any high shear mixers and mills. Second step of particle loadingThis can be done sequentially, where different types of submicron and nanoparticles are deposited sequentially on the surface of the same carrier particle, or two or more types of submicron and/or nanoparticles can be added simultaneously on the surface of the same carrier particle (fig. 7 d). Alternatively, the SiO-containing coating may be applied by suspending nanoscale particles in water₂A moisture-absorbing layer of (a) and (b) bonded or pozzolan micro-sized carrier particles (figure 7 a).

The dry particle coating can be carried out on any dry particle coating equipment, such as commercially available surface modification equipment, e.g., from Nara^TMHybrid (2)^TMFrom Hosokawa Micron^TMHas been prepared by the Mechanofusion^TMAnd Cyclomix^TMSystem, from MAIC^TMMagnetic assisted impact coater (Aveka)^TMEtc.), among others, various types of high shear mixers. Specifically, in the dry particle coating process step, larger cement or pozzolan "carrier particles" (typically in the 10-100 micron range) "are mechanically coated with guest" loading "microparticles and/or guest nanoparticles (ground quartz-typically in the 1 to 20 micron range, silica fume-0.1 to 3 micron range and nanoparticles 1 to 100 nanometers). Furthermore, when the quartz powder used for the first (inner) layer is used as the larger loaded particle and the smaller silicon powder or particles are used for the second layer coating, then the cement particles can be multi-layer coated, while optionally the smallest nano-sized particles are loaded to produce cement particles. An outer third layer. In another embodiment, submicron SCM particles that have been coated with nanoscale particles can be used to coat cement particles (fig. 7 d).

The purpose and characteristic of the dry powder coating process is to cover the larger host particles (also referred to as carrier particles) by a discrete monolayer of smaller guest particles (also referred to as load particles) and to provide a strong (physical or chemical) bond between the host and guest particles due to the close contact with each other. The adhesion forces between particles are mainly due to van der waals forces, electrostatic forces and stronger intermolecular attraction forces. In particular, the dry particle coating process can generally be divided into the following three stages: (1) a de-agglomeration/dispersion phase, wherein the guest submicron or nanoscale guest particle agglomerates are broken down by strong mechanical forces, such as impact, shear and compression forces, and due to particle collisions; (2) an ordered mixing stage in which the dispersed sub-micron and nano-scale particles adhere to the larger micro-scale bulk cement and pozzolan particle surfaces by interparticle forces, such that the larger particle surfaces are loosely covered by the smaller particles; (3) the particles are embedded in a coating, wherein the surface coverage is more durable due to stronger physical (or chemical) bonding between the host and guest particles. The method involves the use of forces that overcome the strong intermolecular forces of attraction between the aggregated particles and bind the larger host and smaller guest particles together, thereby providing maximum packing density. Thus, the method may be referred to as "forced filling of a multi-component cement composition". The "forced filling" method may include considering the powder components as "ideal" non-agglomerated powders, calculating the optimum proportions of the powder components, and then applying impact, shear and compression forces sufficient to break up "real" agglomerates without breaking up individual particles and providing a larger particle coating of smaller particles.

The method of coating submicron and nanoscale SCM particles onto larger micron-sized carrier particles can be substituted for dry powder coatings by using functional polymers for concrete (water reducing agents, retarders, etc.) as binders to fix a single layer, multiple layers, or stack of small-loaded particles onto larger carrier particles. When introduced, the polymer is a liquid and subsequently solidifies to form bridging forces that hold the carrier and loaded particles together in addition to the intermolecular forces described above (fig. 9). Another advantage of coating with a polymer, as opposed to using a dry powder coating, is the ability to coat large quantities of SCM particles and attach the chemically blended polymer to a cementitious or pozzolan matrix carrier. Where a dry coating is used, the number of smaller SCM loaded particles covering the larger carrier particles is limited. Specifically, the SCM particles cover the carrier cement and, if pozzolan particles are present (fig. 2), are no more than about a monolayer (fig. 3-5). However, the use of liquid chemical admixtures allowed multilayering of SCM-loaded particles (fig. 6-9). The chemical admixture acts as a binder to immobilize the multiple layers of "load" particles on the "carrier" particles.

The application of submicron and nanoscale SCM particles to larger micron sized cementitious and pozzolan particles results in a more uniform particle distribution with preferred particle packing density and therefore a denser and stronger mortar/concrete matrix. In this process, finer particles of submicron size (e.g., silicon powder) and nanoscale materials (e.g., nanosilica, carbon nanotubes, nano-TiO)₂Etc.) will disaggregate and bind to particles (e.g., cement and fly ash) in cementitious and pozzolans without the possibility of reagglomeration. The loaded particles adhere to the cementitious/pozzolanic carrier so that when handling the macroscopic cement powder in the dry state, their mutual movement is not wiped away by internal friction between the particles.

One exemplary advantage of this treatment method of coating the cementitious and pozzolan particles (if present) with smaller siliceous particles is also that the cement particles of the macroscopic cement are covered by submicron particles and nanoscale SCM particles formed around the cement particle layer, which forms a submicron or nanometer mesh on the cement surface (fig. 6, 7). The mesh absorbs the moisture of the liquid admixture, thereby protecting the cement particles, preventing the moisture from directly permeating into the cement particles in a large amount, and preventing the cement from being prematurely hydrated. The mesh allows for gradual controlled penetration of moisture to the surface of the cement particles, thereby forming a nano-mesh-calcium silicate hydrate (C-S-H) of cement hydration product on the surface of the cement particles. The nano C-S-H meshes are kept on the surface of cement in the granulation process and are kept in the particles, and play an important role in accelerating the hardening of fresh macroscopic cement.

The production of the macroscopic cement in engineered form, e.g. granular, spherical, agglomerated or pressed, also comprises a subsequent step of granulating, spheroidizing, briquetting or pressing the macroscopic cement, which may optionally be subsequently used in water with other building aggregates for subsequent casting and hardening. Such macroscopic cement-forming processes may use a liquid polymer binder that is mixed with cement particles coated with micro-and/or nano-particles to form inter-particle bonds between the particles, and to agitate the wetted powder to promote particle growth.

Specifically, the engineering process of pelletizing, spheronizing, briquetting or tabletting macroscopic cements using liquid polymeric binders results in the agglomeration of wet particles and the subsequent adhesion and agglomeration of other individual particles onto the agitated moving agglomerates (fig. 10, fig. 12). For example, fig. 10 shows a cross-sectional view of macroscopic cement particles agglomerated (granulated) by tumbling. Figure 11 shows a cross-sectional view of macroscopically large cement particles agglomerated (granulated) by extrusion. Figure 12 shows a method of engineering macroscopic cements by tumbling granulation and by tumbling granulation (agglomeration). Fig. 12(a) shows a method of granulating a large cement tumbled by agglomeration under the action of intermolecular forces. As shown in fig. 12(a), the macroscopic cement powder (1200) comprises cementitious and pozzolan particles supported by submicron and nanoparticles with a chemical admixture as a binder. Fig. 12(b) shows an example of macroscopic cement engineered particles (agglomerates) (1202) produced by tumbling (1204).

The production of engineered granular, spherical, agglomerated or pressed macroscopic cements can also be carried out without the use of binders (fig. 14, 15). By utilizing macroscopic cements produced in a process of forcibly filling a multi-component cementitious composition by dry particle coating and/or filling cementitious or pozzolan micron-sized carrier particles with smaller SCM particles, the use of a binder engineered form of the macroscopic cement in production is not necessary, but may be necessary for tumbling (fig. 12) and preferred for compaction by pressing (fig. 13) and not necessary for compaction by compression (fig. 14, fig. 15).

Referring now to fig. 13, fig. 13(a) illustrates a method of compacting a macro-cement granulation by pressing. Agglomeration occurs within the extrusion die (1302) by a compaction force (1300). The macro-cement powder (1304) is particles of cementitious and pozzolan that are all coated or loaded with submicron and/or nanoparticles that are free of chemical admixtures or that comprise chemical admixtures and optionally sand and aggregate. The method produces macroscopic cement particles (1306). Fig. 13(b) shows engineered macroscopic cement particles produced by compaction/extrusion.

Referring now to fig. 14, fig. 14(a) illustrates a method of compacting a macroscopic cementitious compact by compression. Agglomeration occurs under compressive forces (1400) between compaction rollers (1402) having surface agglomerate-like voids (1404) or pockets. The macro-cement powders (1406) are particles of cementitious and pozzolan that are all coated or loaded with submicron and/or nanoparticles free of or containing chemical admixtures and optionally sand, aggregate and fibers. The method produces macroscopic cement agglomerates (1408). Figure 14(b) shows a macroscopic cement mass produced by compaction/compression.

Referring now to fig. 15, fig. 15(a) illustrates a method of making a macroscopic cementitious compact by compaction/compression. Agglomeration occurs under compressive force (1500) between smooth engineered compaction rollers (1502). The macroscopic cement powders (1504) are particles of cementitious and pozzolan that are all coated or loaded with submicron and/or nanoparticles free of or containing chemical admixtures and optionally sand, aggregate and fibers. The process produces macroscopic cement agglomerates (fractured zones) (1506). Figure 15(b) shows a macroscopic cement mass produced by compaction/compression, wherein the mass (broken up tape) contains reinforced steel microfibers.

The combination of pressure and shear forces applied to the mixture of cement and pozzolan particles and smaller submicron SCM particles (with or without binder) changes the physicochemical properties of the loaded cement and pozzolan particles and increases the strength of intermolecular attraction between all particles in the macroscopic cement. The mechanical action generates a shear-inducing pressure which is used to coat and/or load the cement particles and to generate their physicochemical activation. Thus, the mechanical process of forced filling the dry particle coating and loading using high energy agitation causes physicochemical activation of the macroscopic cement, which may be further referred to as mechanical/physicochemical activation. Furthermore, mechanical/physicochemical activation promotes inter-particle bonding in the subsequent production of the engineered solid macroscopic cement form. In the case of dry particle coatings used in macro-particulate cement production, mechanical/physicochemical activation serves as a substitute for the binder in the granulation, prilling, agglomeration or tabletting process. In the case of the use of a binder, mechanical/physicochemical activation still occurs, but the strength of the interparticle bonds is stronger in the subsequent production of the engineered solid form of macroparticle cement, the binder creating liquid bridges (fig. 9). However, the use of adhesives may not be optimal for all applications. For example, no binder is required in the formation of engineered particles produced in compaction by pressing (fig. 14, 15). In the case of the use of a binder, the SCM particles may protect the cement particles from hydration.

Whether the production of engineered solid form macroscopic cements is carried out in the presence of a binder or under dry particle coated macroscopic cements, one class of process equipment includes rotating drums and pans, fluidized beds and mixing granulators. The compaction granulation process uses a liquid polymer binder that is mixed with cement particles coated with microparticles and/or nanoparticles, and/or pressurized to promote interparticle bonding. Such methods include rolling, extrusion and tabletting (fig. 12-15). The binder provides additional interparticle bonding in the engineered macrocement in the form of macrocement particles, pellets, briquettes, tablets, or other possible solid forms.

In various embodiments, the above methods for producing engineered macrocement may result in the following features. Macroscopic cements can be produced in the form of granules, pellets, agglomerates or sheets by mechanical action, for example by pressure and shear forces which cause physicochemical activation of the cementitious material during its coating and/or loading. The particles may be produced directly during the process of coating and/or loading the cementitious material into the equipment performing the coating and/or loading process, and may have a slightly rounded or slightly rounded and flattened shape and an equivalent spherical diameter of about 1 to about 20 mm. After the coating and/or loading process of the cementitious material, the granules may be produced in a tumbling drum and pan, fluidized bed and mixing granulator, and may have a slightly rounded or slightly rounded and flattened shape and an equivalent spherical diameter of about 1 to about 5 mm. The particles may alternatively have a somewhat rounded or somewhat rounded and flattened shape and an equivalent spherical diameter of about 2 to about 10 mm. After the coating and/or loading process of the cementitious material, the pellets may be produced by extrusion in an extruder or pelletizer and may have a cylindrical shape and an equivalent spherical diameter of about 5 to about 40 mm. After the coating and/or loading process of the cementitious material, the mass or sheet may be produced by compression at a roller with shaped voids, which may have a slightly rounded or somewhat rectangular shape and an equivalent spherical diameter of about 10 to about 50 mm. Alternatively, after the coating and/or loading process of the cementitious material, the agglomerates may be produced by compression from smooth rolls, and the agglomerates may have an irregular fractured zone shape and an equivalent spherical diameter of about 3 to about 30 mm.

One advantage of granulated or pelletized macroscopic cements is that the water contained in the liquid binder causes partial hydration of the cement (3% to 7% of its mass), forming nano-scale hydrates (C-S-H) of the calcium silicate cement particle surface. On the one hand, this phenomenon can be considered as a corresponding loss of cement activity, but on the other hand, the nano C-S-H mesh develops as nano C-S-H seeds during the mixing of the cement with water, resulting in an increase in the reaction rate and early and final strength of the concrete made of the cement-accelerated granular macroscopic cement. As a result of the reaction with the water contained in the liquid polymer binder, the C-S-H mesh formed on the surface of the granules is destroyed during the mixing of the macroscopic cement with water. The substantially complete destruction of the intermediate C-S-H mesh creates nano C-S-H seeds, which is the final goal, which in turn accelerates the hardening of the cement and increases the early and final strength of the hardened cement paste. More specifically, the finely ground C-S-H acts as a crystallization seed, initiating the setting of the cement binder.

Another exemplary advantage of various forms of engineered macroscopic cements is their extended shelf life by coating cement particles with a polymer and then agglomerating several of these particles in different forms (e.g., particles or pellets or lumps or flakes) to greatly reduce the surface area exposed to moisture and carbon dioxide present in the atmosphere, thereby preventing cement hydration and loss of cement activity. Another exemplary advantage of engineered macroscopic cements is the elimination of dust handling hazards and losses. Another exemplary advantage of engineered macrocement is the elimination of separation of the various macrocement components. Another exemplary advantage of the engineered macrocement is improved flow properties for further processing, reducing caking and lump formation. Another exemplary advantage of engineered macroscopic cements is increased bulk density on storage. Another advantage of the engineered macro cement is the ability to produce a stable, non-segregating mixture of powder constituents. Another exemplary advantage of engineered macroscopic cements is the acceleration of the reaction rate in the cement mixture.

In embodiments, the macroscopic cement mixture with optional sand and/or larger aggregate may also be mixed together with reinforcing fibers such as metal fibers (steel, stainless steel, titanium, copper or brass coated steel, etc.), glass fibers, synthetic fibers (polypropylene, polyethylene), carbon fibers, aramid fibers, or natural fibers including but not limited to cellulose and hemp fibers to make a mixture prior to pelletizing, agglomerating or sheeting the mixture. The resulting engineered shaped object, such as a particle, pellet, briquette, or tablet, contains fibers dispersed throughout the macroscopic cement in the engineered solid form (fig. 15 b). Subsequently, when the engineered form of the macroscopic cement with fibers is introduced into the wet mixing process (fig. 16), the fibers are dispersed throughout the macroscopic cement during mixing with water, and then in the solid concrete. The fibers become an integral part of the hardened concrete matrix and act as reinforcing elements for the concrete matrix. Such fibers have significantly different specific gravities, shapes and sizes compared to the other mineral components of the dried multicomponent mixture. The advantage is that the reinforcing microfibres are firmly fixed together with the other constituents inside the granules, pellets, agglomerates or tablets and are uniformly distributed in the dry multicomponent mixture from the production of the granules to the homogenization with water.

During dry coating and/or loading of macroscopic cements, the surface of the fibers is scratched and scraped by the sharp and hard sand and/or aggregates and causes the fibers to be forced recessed on the surface (fig. 31, fig. 32). Scraped and scraped fibers have improved bond slip properties compared to virgin smooth metal fibers or other fibers that cannot be scraped or scraped in known mixers with aggregate and sand particles. The impression on the fibers in the macroscopic cement improves the strength and durability of the concrete. The indentation and scratching of the steel fibers may improve the mechanical adhesion between the fibers and the cement matrix. An example of scraped and pitted fibers is shown in fig. 31. FIG. 31 shows Scanning Electron Microscope (SEM) images at various magnifications of steel reinforcing fibers scratched and depressed during a course cement dry coating process; FIG. 31(a) shows an SEM image at 200 magnification of steel reinforcing fibers of 6mm length and 0.16mm diameter scraped and depressed during macro cement dry coating; FIG. 31(b) shows an SEM image at 400 magnification of steel reinforcing fibers of 6mm length and 0.16mm diameter scraped and depressed during macro cement dry coating; FIG. 31(c) shows an SEM image at x 800 magnification of steel reinforcing fibers having a length of 6mm and a diameter of 0.16mm that were scratched and dented during macro cement dry coating; fig. 31(d) shows an SEM image at x 1600 magnification number of steel reinforcing fibers 6mm in length and 0.16mm in diameter that were scratched and dented during macro cement dry coating.

The indentations, scratches and dents on the fibers are filled and coated with cement and silica fume particles and optionally with a binder, providing chemical adhesion between the fibers and the cement matrix in addition to mechanical adhesion. FIG. 32 shows Scanning Electron Microscope (SEM) images at various magnifications of steel reinforcing fibers scratched and depressed during macroscopic cement loading; FIG. 32(a) shows SEM images at x 200 magnification of steel reinforcing fibers of 6mm length and 0.16mm diameter scraped and dented during macroscopic cement loading and cement and silica fume attached to the fiber surface; FIG. 32(b) shows an SEM image at 400 magnification of steel reinforcing fibers of 6mm length and 0.16mm diameter scraped and depressed during macroscopic cement loading and cement and silica fume attached to the fiber surface; FIG. 32(c) shows an SEM image at x 800 magnification of steel reinforcing fibers of 6mm length and 0.16mm diameter scraped and depressed during macroscopic cement loading and cement and silica fume attached to the fiber surface; figure 32(d) shows SEM images at 1600 magnification of steel reinforcing fibers 6mm in length and 0.16mm in diameter that scrape and dent during macroscopic cement loading and cement and silica fume attachment on the fiber surface.

A multi-stage homogenization process for preparing a cementitious material from dried or granulated macroscopic cement is also provided (fig. 28-30). In particular, the method includes homogenizing dry macro-cement or engineered forms of macro-cement in water at high energy levels to form a cement slurry, and homogenizing the macro-cement water slurry with sand and/or larger aggregates in a subsequent step.

Figure 28 illustrates various process flow options for producing macro cement by dry coating and preparing concrete from the macro cement using a multi-stage homogenization process. For example, fig. 28(a) shows a process flow diagram illustrating the production of macroscopic cement by dry coating (2800) the micron-sized cement (2802) and pozzolan particles (2804) with submicron (2806) and nanoparticles (2808), using a powerful homogenizer (2810) to which a chemical admixture (2812) can be applied, and then mixing the macroscopic cement slurry with sand (2814), aggregate (2816), and/or fibers (2818) in a lower energy mixer (2820) to make concrete.

Fig. 28(b) shows a process flow diagram illustrating the production of macroscopic cement by dry coating (2800) the micron cement (2802) and pozzolan particles (2804) with submicron (2806) and nanoparticles (2808), adding a chemical admixture (2812) to a homogenizer (2810), high strength homogenization of the macroscopic cement powder in water, mixing the macroscopic cement slurry with sand (2814) in a low energy mixer (2822), and then mixing the macroscopic cement mortar with aggregate/fiber in a lower energy standard mixer (2820) to make concrete.

Fig. 28(c) shows a process flow diagram illustrating the production of macroscopic cement by dry coating (2800) the micron cement (2802) and pozzolan particles (2804) with submicron (2806) and nanoparticles (2808), engineering the macroscopic cement powder (2826) into particles/pellets/lumps, adding a chemical admixture (2812) to a homogenizer (2810), highly homogenizing the particles in water, and then mixing the macroscopic cement slurry with sand (2814), aggregate (2816), and/or fibers (2818) in a lower energy mixer (2820) to make concrete.

Fig. 28(d) shows a process flow diagram illustrating the production of macroscopic cement by dry coating (2800) the micron cement (2802) and pozzolan particles (2804) with submicron (2806) and nanoparticles (2808), engineering the macroscopic cement powder (2826) into particles/pellets/lumps, adding chemical admixture (2812) to homogenizer (2810), highly homogenizing the particles in water, then mixing the macroscopic cement slurry with sand (2814) in low energy mixer (2822), then mixing the macroscopic cement mortar with aggregate (2816) and/or fibers (2818) in lower energy standard mixer (2820) to make concrete.

Figure 29 illustrates various process flow options for producing macrocement by coating a micron-sized cement with or without pozzolan particles with submicron and nanoparticles in the presence of a chemical admixture and making concrete from the macrocement using a multistage homogenization process. For example, fig. 29(a) shows a process flow diagram illustrating the production of macroscopic cement by coating 2900 micron-sized cement (2902) and pozzolan particles (2904) with submicron-sized (2906) and nanoparticles (2908) and a chemical admixture (2912), homogenizing the macroscopic cement powder in water with a powerful homogenizer (2910), and then mixing the macroscopic cement slurry with sand (2914), aggregate (2916), and/or fibers (2918) in a lower energy mixer (2920) to make concrete.

Fig. 29(b) shows a process flow diagram illustrating the production of a macroscopic cement by coating 2900 the micron-sized cement (2902) and pozzolan particles (2904) with a submicron-sized (2906) and nanoparticles (2908) and a chemical admixture (2912), homogenizing the macroscopic cement powder in water with an intensive homogenizer (2910), mixing the macroscopic cement slurry with sand (2914) in a lower energy density mixer (2926), and then mixing the macroscopic cement mortar with aggregate (2916) and/or fibers (2918) in a lower energy standard mixer (2920) to make concrete.

Fig. 29(c) shows a process flow diagram illustrating the production of macroscopic cement by coating 2900 micron-sized cement (2902) and pozzolan particles (2904) with sub-micron-sized (2906) and nanoparticles (2908) and a chemical admixture (2912), engineering (2928) the macroscopic cement powder into particles/pellets/lumps, homogenizing the macroscopic cement powder in water with an intensive homogenizer (2910), and then mixing the macroscopic cement slurry with sand (2914), aggregate (2916), and/or fibers (2918) in a lower energy mixer (2920) to make concrete.

Fig. 29(d) shows a process flow diagram illustrating the production of macroscopic cement by coating 2900 micron-sized cement (2902) and pozzolan particles (2904) with submicron-sized (2906) and nanoparticles (2908) and chemical admixture (2912), engineering (2928) macroscopic cement powder into particles/pellets/lumps, homogenizing the macroscopic cement powder in water with an intensive homogenizer (2910), mixing the macroscopic cement slurry with sand (2914) in a low energy mixer (2926), and mixing the macroscopic cement mortar with aggregate (2916) and/or fibers (2918) in a lower energy standard mixer (2020) to make concrete.

Fig. 30 shows two process flow options for producing macroscopic cement by coating a micro-sized cement (3002) with or without pozzolan particles (3004) with sub-micron (3006) and nano-particles (3008) in the presence of a chemical admixture (3010) and also adding sand (3012), aggregate (3014), and/or fibers (3016) and optionally performing macro-cement powder engineering (3018) into particles/pellets/agglomerates (as shown in fig. 30(b) but omitted in fig. 30 (a)), and making concrete from the macroscopic cement by a multistage homogenization process (3020) comprising mixing the macroscopic cement particles with water to make concrete.

Optionally, the sand and/or aggregate may also be coated with cure accelerating additives such as calcium chloride, triethanolamine, sodium thiocyanate, sodium formate/calcium, sodium nitrite/calcium, calcium nitrate, aluminates, and silicates. The amount of cure accelerating admixture may range from about 0.1% to about 20% by weight of the cementitious material, and in most applications, preferably from about 0.5% to about 10% by weight of the cementitious material.

Mixing a homogenized suspension of homogenized cement in water with larger sized aggregates allows for the subsequent casting of shaped elements or structures and hardening of the subject.The aggregate used herein may be any conventional mineral aggregate, such as sand or a mixture of sand with gravel, crushed stone or equivalent material. The crushed stone can be limestone, basalt, granite, bauxite, etc. In addition, a mathematical model is provided that considers the rheological properties of macroscopic cement, mortar and concrete mixtures, defines a range of rheological parameters for each mixture, and determines an optimal range of mixing parameters for the mixture based on the respective model. The model described with reference to fig. 18 to 22. FIG. 18 shows the Bingham model, which is based on the yield stress τ₀Shear rate γ and plastic viscosity μ characterize the rheology of the cement.

With the advent of aggregates from macroscopic cement slurries to mortars and the increase in aggregate size and decrease in water content from mortars to concretes, cementitious systems not only increased viscous friction but also internal dry friction between filler particles occurred, increasing with the increase in the number and size of aggregates. Dynamic yield stress tau of macroscopic cement slurries, mortars and concretes₀The difference between the values not only indicates that the macrocement slurry, mortar and concrete should be mixed at different speeds to provide the best homogeneity, but also that they should be mixed in different mixers and preferably under different mixing principles, since in one mixing process the speed control and the variation of the design parameters cannot account for the essential differences in the rheological properties of the macrocement slurry, mortar and concrete and it is necessary to design their mixing process according to their respective rheological properties (fig. 21, fig. 22). An efficient mixing process (without segregation and separation of the components to maximize homogeneity of the mixture) of cementitious products occurs at shear stress of the product at dynamic yield stress τ₀Ultimate dynamic stress tau corresponding to a structure of complete failure of the cementitious product_dWithin the range of (a): tau is_{0 macroscopic cement}＜τ＜τ_dWherein in some cases the dynamic stress τ is limited_dPossible specific dynamic yield stress tau₀One order of magnitude higher, which can be obtained by the following equation τ₀<τ<10τ₀Although in most cases within the corresponding shear rate γ range, the dynamic stress τ is limited_dAbout dynamic yield stress tau₀Four times that of the prior art. It is taught that the shear rate γ is proportional to the yield stress τ mixing speed (rpm) and depends on the design parameters of the mixer.

Furthermore, unlike the conventional practice of mixing cement with water, the addition of a dry cementitious macro-cement mixture to high energy flowing water is a preferred method of making hardened concrete members or structures from macro-cement mixtures or macro-cements in engineered form. Specifically, the macroscopic cement is injected into the energized moving water stream such that the ratio of macroscopic cement to water and the amount of water are sufficient to produce a suspension of macroscopic cement slurry having a uniform distribution of water and cement components, as opposed to a dense conventional cement slurry. The mixing energy density should be sufficient to uniformly and sufficiently disperse the cement particles and to homogenize the cement with water simultaneously by high shear (shear rate γ provides the shear stress equation τ₀＜τ＜10τ₀And in most cases at τ₀＜τ＜4τ₀Within) having an energy density sufficient to uniformly and sufficiently disperse cement particles without segregation and separation of the components. Thus, the mixing should be at shear rate γ_{Macroscopic cement}Providing shear stress τ_{0 macroscopic cement}＜τ＜10τ_{0 macroscopic cement}Is carried out in most cases at τ_{0 macroscopic cement}＜τ＜4τ_{0 macroscopic cement}Within the range of (1). For example, the body of water and the subsequent hydraulic cement suspension may be powered by a high pressure nozzle, a rotor-stator mixer, a venturi system, or an ultrasonic processor. In all of these systems, the input energy is converted into friction, turbulence, micro-turbulence, waves, microwaves and cavitation, thereby promoting homogenization and substantial homogenization of the cement. The subsequent step consists in mixing in water the homogenized suspension of the macrocement with sand and/or aggregate of larger size in a mixer with (lower) mixing energy density for homogenizing the macrocement and said sand and/or aggregate mixture (in the case of mortars, the shear stress provided by the shear rate γ is τ_{0 mortar}＜τ＜10τ_{0 mortar}In most cases, at τ_{0 mortar}＜τ＜4τ_{0 mortar}Within the range, or in the case of concrete, the shear stress provided by the shear rate γ is τ_{0 concrete}＜τ＜10τ_{0 concrete}And in most cases at τ_{0 concrete}＜τ＜4τ_{0 concrete}Within range), a fourth step of casting the shaped element or structure and hardening the subject.

Mixing methods with different energy densities may include mixing of multiphase dry powder/bulk concrete materials in different stages by dividing the entire heterogeneous continuum into groups, each group having similar material cohesion and the cohesion being different between groups. (fig. 28-30) the method may further include first mixing a group of materials with the highest cohesion with water through a system with the highest energy density corresponding to substantially complete homogenization of the materials in that particular group, and then adding to that group. The more homogenized material, which has a lower cohesion, is mixed together by the system with the lower energy density, so that the whole group is substantially homogenized. Then, if necessary, a larger material (with a correspondingly reduced cohesion) is added to the new homogenized material and the total volume of material is mixed by a system with an even lower energy density (corresponding to a substantially complete homogenization of the new whole group).