Structure of reinforced cementitious material and process of making the same structure by a three-dimensional printing process
11529751 · 2022-12-20
Inventors
- Domenico Asprone (Naples, IT)
- Ferdinando Auricchio (Milan, IT)
- Costantino Menna (Carbonara di Nola, IT)
Cpc classification
E04B5/08
FIXED CONSTRUCTIONS
E04B2/18
FIXED CONSTRUCTIONS
B28B1/001
PERFORMING OPERATIONS; TRANSPORTING
E04C2/041
FIXED CONSTRUCTIONS
B28B23/22
PERFORMING OPERATIONS; TRANSPORTING
International classification
E04B2/18
FIXED CONSTRUCTIONS
B28B1/00
PERFORMING OPERATIONS; TRANSPORTING
Abstract
A structure has a plurality of modules of cementitious material; a first module exhibiting a reciprocal coupling surface and hooking portions defining at least one cavity, a second module exhibiting a respective reciprocal coupling surface—countershaped and in contact with the reciprocal coupling surface of the first module—and a hooking portion defining at least one cavity extending along at least partially the stratification direction; a connecting element engaged, on one side, inside the cavity of the hooking portion of the first module and, on the other side, inside the cavity of the hooking portion of the second module. The connecting element is configured for stably constraining the first and second modules and holding these latter in contact with each other. Further, a process makes a structure of reinforced cementitious material.
Claims
1. A process of making a structure of reinforced cementitious material comprising the following steps: making, by a three-dimensional printing process, a plurality of modules of cementitious material, said three-dimensional printing process comprising a step of depositing a plurality of layers of cementitious material one on another according to a stratification direction, said plurality of modules comprising: at least one first module comprising at least one lateral wall delimited by an outer surface and extending along the stratification direction, at least part of said outer lateral surface of the first module defining a reciprocal coupling surface, said first module further comprising at least one hooking portion defining at least one cavity extending at least partially along the stratification direction, and at least one second module comprising at least one lateral wall delimited by an outer surface and extending along the stratification direction, at least part of the outer surface of the second module defining a reciprocal coupling surface countershaped to the reciprocal coupling surface of the outer surface of the first module, said second module further comprising at least one hooking portion defining at least one cavity extending at least partially along the stratification direction; bringing in contact the first and second modules so that respective coupling reciprocal surfaces of the first and second modules abut on each other; following the step of contacting the first and second modules, engaging at least one connecting element, on one side, inside the cavity of the hooking portion of the first module and, on another side, inside the cavity of the hooking portion of the second module, said connecting element constraining the first and second modules and being configured for holding the first and second modules in contact with each other, wherein the connecting element comprises: at least one reinforcing bar extending along a longitudinal development direction between a first and second end portions, at the first end portion, a first engagement portion emerging from the reinforcing bar transversally to the longitudinal development direction of the reinforcing bar, and at the second end portion, a second engagement portion emerging from the reinforcing bar transversally to the longitudinal development direction of the reinforcing bar, wherein the first and second engagement portions of the connecting element are distinct and removably associable to the reinforcing bar, engaging the first and second engagement portions in the first and second modules respectively; and after engaging the first and second engagement portions in the first and second modules, constraining the reinforcing bar to said first and second engagement portions, wherein the step of engaging the connecting element to the first and second modules comprises the following sub-steps: engaging the first engagement portion inside the cavity of the hooking portion of the first module, and engaging the second engagement portion inside the cavity of the hooking portion of the second module.
2. The process according to claim 1, wherein the step of engaging the first engagement portion to the first module comprises at least the following sub-steps: inserting the first engagement portion inside the cavity of the hooking portion of the first module, filling at least partially the cavity of the hooking portion of the first module with a cementitious material at least partially at a liquid state so that the cementitious material can contact at least part of said first engagement portion, constraining, by hardening the cementitious material inside the cavity of the first module, said first engagement portion, and wherein the step of engaging the second engagement portion to the second module comprises at least the following sub-steps: inserting the second engagement portion inside the cavity of the hooking portion of the second module, filling at least partially the cavity of the hooking portion of the second module with a cementitious material at least partially at a liquid state so that the cementitious material can contact at least part of said second engagement portion, constraining, by hardening the cementitious material inside the cavity of the second module, said second engagement portion.
3. The process according to claim 1, comprising, after the step of engaging the connecting element with the first and second modules, a further step of fixing the first and second modules having the following sub-steps: providing between the reciprocal coupling surfaces of the first and second modules, a predetermined quantity of cementitious material at least partially at a liquid state, further constraining, by hardening said cementitious material disposed between the reciprocal coupling surfaces, said first and second modules.
4. The process according to claim 1, wherein the step of depositing, by a three-dimensional printing process, the plurality of layers of cementitious material one on another according to the stratification direction, comprises a superimposing of layers exhibiting substantially a same shape and size, each module exhibiting, according to the stratification direction, a substantially constant cross-section for defining a profile.
5. The process according to claim 1, wherein the lateral wall of the first module defines a closed outer perimeter, and the lateral wall of the second module defines a closed outer perimeter, the hooking portion of said first module is defined inside said closed outer perimeter and extends for all a development of the first module along the stratification direction, the hooking portion of said second module is defined inside said closed outer perimeter and said hooking portion extends for all a development of the second module along the stratification direction.
6. The process according to claim 1, wherein the step of depositing the cementitious material by the three-dimensional printing, is adapted to define a first hollow module with a closed outer perimeter, said depositing step further comprising a step of defining, inside the closed outer perimeter of the first module, a reinforcing portion, said reinforcing portion extending inside the closed outer perimeter of the first module between two sides of said closed outer perimeter, substantially opposite to each other.
7. The process according to claim 6, wherein the reinforcing portion extends along the stratification direction of the first module and defines, cooperatively with the lateral wall of the first module, at least one first and one second through seats.
8. The process according to claim 1, wherein the step of depositing the cementitious material by the three-dimensional printing, defines a second hollow module having a closed outer perimeter, said depositing step further comprising a step of defining, inside the closed outer perimeter of the second module, a reinforcing portion, said reinforcing portion extending inside the closed outer perimeter of the second module between two sides of said closed outer perimeter substantially opposite to each other.
9. The process according to claim 8, wherein the reinforcing portion of the second module extends along the stratification direction of the second module itself and defines, cooperatively with the lateral wall of the second module, at least one first and one second through seats.
10. The process according to claim 1, wherein the second module comprises a further reciprocal coupling surface opposite to the reciprocal coupling surface of the second module, said plurality of modules comprises at least one third module comprising at least a lateral wall delimited by an outer surface and extending along the stratification direction, at least part of the outer surface of the third module defining a reciprocal coupling surface countershaped to the further reciprocal coupling surface of the second module, said third module further comprising at least one hooking portion defining at least one cavity extending at least partially along the stratification direction, said process further comprising the following steps: bringing in contact the second and third modules so that the further reciprocal coupling surface of the second module and the reciprocal coupling surface of the third module abuts on each other, the third module being opposite to the first module with respect to the second module, after the step of contacting the second module with the third module, engaging at least one connecting element, on one side, inside the cavity of the hooking portion of the second module and, on another side, inside the cavity of the hooking portion of the third module, said connecting element constraining the second module and third module, and being configured for holding the second and third modules in contact with each other.
11. The process according to claim 10, wherein the connecting element of the second and third modules comprises at least one reinforcing bar extending along a longitudinal development direction between a first and second end portions, said connecting element comprising—at the first end portion—a first engagement portion emerging from the reinforcing bar transversally to the longitudinal development direction of the reinforcing bar, said connecting element further comprising—at the second end portion—a second engagement portion emerging from the reinforcing bar transversally to the longitudinal development direction of the reinforcing bar, the step of engaging the connecting element with the second and third modules comprises at least the following sub-steps: engaging the first engagement portion inside the cavity of the hooking portion of the second module, engaging the second engagement portion inside the cavity of the hooking portion of the third module.
12. The process according to claim 11, wherein the step of engaging the first engagement portion with the second module comprises at least the following sub-steps: inserting the first engagement portion inside the cavity of the hooking portion of the second module, filling at least partially the cavity of the hooking portion of the second module with a cementitious material at least partially at a liquid state so that the cementitious material can contact at least part of said first engagement portion, constraining, by hardening the cementitious material inside the cavity of the second module, said first engagement portion, and wherein the step of engaging the second engagement portion with the third module comprises at least the following sub-steps: inserting the second engagement portion inside the cavity of the hooking portion of the third module, filling at least partially the cavity of the hooking portion of the third module with a cementitious material at least partially at a liquid state so that the cementitious material can contact at least part of said second engagement portion, constraining, by hardening the cementitious material inside the cavity of the third module, said second engagement portion.
13. The process according to claim 11, wherein the first and second engagement portions of the connecting element of the second and third modules, are distinct and removably associated to the reinforcing bar, the process comprises the steps of engaging said first and second engagement portions respectively in the second and third modules and after a step of constraining the reinforcing bar to said first and second engagement portions.
14. The process according to claim 10, wherein the lateral wall of the third wall defines a closed outer perimeter, wherein the hooking portion of the third module is defined inside said closed outer perimeter, and said hooking portion extends for all a development of the third module along the stratification direction.
15. The process according to claim 10, wherein the step of depositing the cementitious material by the 3D printing, defines a third hollow module having a closed outer perimeter, said depositing step further comprising a step of defining, inside the closed outer perimeter of the third module, a reinforcing portion, said reinforcing portion extending inside the closed outer perimeter of the third module between two sides of said closed outer perimeter, substantially opposite to each other, wherein the reinforcing portion extends along a stratification direction of the third module and defines, cooperatively with the lateral wall of the third module, at least one first and one second through seats.
16. The process according to claim 10, comprising the step of engaging at least one connecting element, on one side, inside the cavity of the hooking portion of the first module and, on another side, inside the cavity of the hooking portion of the third module, said connecting element constraining the first module and third module.
17. The process according to claim 1, wherein the process comprises—after the step of engaging the connecting element with the second and third modules—a step of further fixing the second and third modules which provides at least the following sub-steps: providing between the further reciprocal coupling surface of the second module and the reciprocal coupling surface of the third module, a predetermined quantity of a cementitious material at least partially at liquid state, and further constraining, by hardening said cementitious material disposed between said further reciprocal coupling surfaces, said second and third modules.
18. The process according to claim 1, wherein the step of depositing, by a three-dimensional printing process, the plurality of layers of cementitious material, one on another along the stratification direction comprises a step of overlapping layers exhibiting substantially a same shape and size, each module exhibiting, along the stratification direction, a substantially constant cross-section for defining a profile.
Description
DESCRIPTION OF THE DRAWINGS
(1) Some embodiments and some aspects of the invention will be described in the following with reference to the attached drawings, given only in an indicative and therefore non-limiting way, wherein:
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(10) FIGS. from 12 to 16 schematically illustrate some steps of a process of making a structure of reinforced cementitious material according to the present invention;
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DETAILED DESCRIPTION
(14) It is noted that in the present detailed description, corresponding parts illustrated in the different figures are indicated by the same numeral references. The figures could illustrate the object of the invention by not-to-scale representations; therefore, parts and components illustrated in the figures regarding the object of the invention could refer only to schematic representations.
(15) The term “three-dimensional printing” or 3D printing means a process of making objects by a three-dimensional printer or 3D printer based on a material additive technology (known as Additive Manufacturing). The process provides making—by dedicated modelling software—a three-dimensional model which is delivered to a 3D printer configured for making the corresponding physical model of the digital mathematical model by depositing a material one layer on another, by advancing by cross-sections towards the top.
(16) The term “3D printer” means a device configured for making a three-dimensional physical model by means of an additive manufacturing 3D-printing process. Particularly, the 3D printer comprises at least one supplying head 101 configured for depositing a predetermined quantity of material. The 3D printer comprises a movement system 102 connected to the supplying head 101 which is configured for moving this latter according to a three-dimensional space.
(17) Moreover, the 3D printer can comprise a control unit 103 connected to the movement system 102 and to the supplying head 101; the control unit 103 is configured for receiving and processing a digital mathematical model and for commanding the activation of the movement system 102 and supplying head 101 for defining the stratification (layer-by-layer) of the processed model. The 3D printer is configured, starting from an object designed/drawn by software, for physically reproducing it by suitable materials.
(18) The term “control unit” 103 means an electronic-type component which can comprise at least one of: a digital processor (CPU), a memory (or memories), an analog-type circuit, or a combination of one or more digital processing units with one or more analog-type circuits. The control unit can be “configured” or “programmed” for executing some steps: this can be physically obtained by any means enabling to configure or program the control unit. For example, when a control unit comprises one or more CPUs and one or more memories, one or more programs can be stored in suitable memory banks connected to the CPU or CPUs; the program or programs contain instructions which, when are executed by the CPU or CPUs, program or configure the control unit for executing operations described with reference to the control unit. As an alternative, if the control unit is or comprises an analog-type circuitry, then the circuit of the control unit can be designed to include a configured circuitry, when used, for processing electric signals in order to execute the steps regarding the control unit.
(19) The term “cementitious material” means a material comprising at least partially a composition of cementitious material, or a cementitious material as specifically described in the following. Particularly, the term “cementitious material” means a material comprising fully, particularly exclusively, said composition of cementitious material or a cementitious composition. Particularly, the term “cementitious material” means a material obtained by a composition of cementitious material or a cementitious composition as specifically described in the following. Particularly, the cementitious material is obtained by 3D-printing a cementitious composition according to the hereinbelow description.
1. STRUCTURE
(20) 1 generally indicates a structure of reinforced cementitious material, for example, useable in the architectural and building fields, for example for erecting buildings, and also in the construction engineering field. As it is visible for example in FIGS. from 1 to 3, the structure 1 comprises a plurality of modules of cementitious material each of them, as will be better described in the following, is manufacturable by a three-dimensional printing process. More particularly, the structure 1 comprises at least one first module 2 externally delimited by a lateral wall 3 which defines an outer lateral surface 3a of the first module 2. As it is for example visible in
(21) From the dimensional point of view, the first module 2 can exhibit a height—defined along the stratification direction D—greater than 100 mm, particularly greater than 200 mm, still more particularly comprised between 250 and 1,000 mm. Moreover, the first module can exhibit a length and a width—measured perpendicular to the stratification D and perpendicular to each other—greater than 100 mm, particularly greater than 200 mm, still more particularly comprised between 250 and 3,000 mm.
(22) As it is visible in the attached figures, moreover the structure 1 comprises at least one module 5 externally delimited by a lateral wall 6 which defines an outer lateral surface 6a of the second module 5. The lateral wall 6 of the second module 5 extends along a stratification direction between a first and second ends; the stratification direction, as will be better described in the following, is a direction along which the three-dimensional printing process deposits a plurality of layers L of cementitious material one on the other (
(23) From the dimensional point of view, the second module 5 can exhibit a height—defined along the stratification direction of the module 5 itself—greater than 100 mm, particularly greater than 200 mm, still more particularly comprised between 250 and 1,000 mm. In an embodiment illustrated in the attached figures, the first and second modules 2, 5 exhibit substantially the same height: the first and second ends of the first module are respectively disposed at the first and second ends of the second module 5. Moreover, the second module 5 can exhibit a length and width—measured perpendicularly to the stratification direction of the module 5 itself and perpendicular to each other—greater than 100 mm, particularly greater than 200 mm, still more particularly comprised between 250 and 3,000 mm.
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(25) More particularly and as it is visible in the attached figures, the connecting element 8 comprises at least one reinforcing bar, optionally of metal material, extending along a longitudinal development direction between a first and second end portions 8a, 8b: the longitudinal development direction of the bar is transversal, particularly perpendicular, to the stratification direction of the first and second modules. The connecting element 8 comprises—at the first end portion 8a—a first engagement portion 9 emerging from the reinforcing bar transversally to the longitudinal development direction of the same and engaged inside the cavity 4a of the hooking portion 4 of the first module 2. Moreover, the connecting element 8 comprises—at the second end portion 8b—a second engagement portion 10 emerging from the reinforcing bar transversally to the longitudinal development direction of the same and engaged inside the cavity 7a of the hooking portion 7 of the second module 2. De facto, the portions 9 and 10 partially cross—along the height—the first and second modules 2, 5 while the reinforcing bar is disposed outside the lateral wall and the through seat of the respective modules. The reinforcing bar is essentially an outer connecting bar between the portions 9, 10 which are engaged inside the respective modules; the bar essentially acts as a tie in relation to the tensile stresses generated in the system. Moreover, the connecting element 8 can comprise only one reinforcing bar adapted to connect the engagement portions 9 and 10.
(26) The structure 1 can comprise only one connecting element 24 adapted to constrain the second and third modules 5, 18 (
2. PROCESS
(27) Moreover, it is an object of the present invention a process of making a structure 1 of reinforced cementitious material according to any one of the attached claims and/or according to the above given description. The process comprises a step of making a plurality of modules of cementitious material by a three-dimensional printing process which comprises a step of depositing a plurality of layers L of cementitious material one on the other along a stratification direction D; the layers L exhibit substantially the same shape and size: each module can exhibit, along the stratification direction D, a substantially constant cross-section for essentially defining a profile. However, it is not excluded the possibility of making modules exhibiting—along the stratification direction D—a varying cross-section, obtainable, for example, by a “cantilevered” layer-by-layer printing process. Particularly, by the three-dimensional printing process, the first and second modules 2, 5 and optionally also the third module 18 are obtained.
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(29) As hereinbefore described, the connecting element 8 can comprise engagement portions 9, 10 distinct and removable from the reinforcing bar; in such arrangement, the step of engaging the connecting element 8 comprises the following sub-steps: inserting the first engagement portion 9 inside the cavity 4a of the hooking portion 4 of the first module 2, filling at least partially the cavity 4a of the hooking portion 4 of the first module 2 with a cementitious material at least partially at a liquid state so that this latter can contact at least part of said first engagement portion 9, constraining, by hardening the cementitious material inside the cavity 4a of the first module 2, said first engagement portion 9, inserting the second engagement portion 10, for example before a step of hardening the cementitious material present in the cavity 4a, inside the cavity 7a of the hooking portion 7 of the second module 5, filling at least partially the cavity 7a of the hooking portion 7 of the second module 5 with a cementitious material at least partially at a liquid state so that this latter can contact at least part of said second engagement portion 10, constraining, by hardening the cementitious material inside the cavity 7a of the second module 5, said second engagement portion 10.
(30) After engaging the engagement portions 9, 10 with the modules 2 and 5, the process comprises a step of constraining (fixing) the reinforcing bar to said first and second engagement portions 9, 10. The process, simultaneously with or after the step of engaging the connecting element 8 with the first and second modules, can comprise at least one step of further fixing the first and second modules which comprises at least the following sub-steps: providing between the reciprocal coupling surfaces of the first and second modules, a predetermined quantity of cementitious material at least partially at a liquid state, further constraining, by hardening said cementitious material disposed between the reciprocal coupling surfaces, said first and second modules.
(31) If a third module 18 is present, moreover the process can comprise a step of engaging at least one connecting element 24, on one side, inside the cavity 7a of the hooking portion 7 of the second module 5 and, on the other side, inside the cavity 20a of the hooking portion 20 of the third module 18; the connecting element 24 stably constrains the second module 5 and third module 18 and is configured for holding these latter in contact with each other. More specifically, the step of engaging the connecting element 24 with the second and third modules comprises at least the following sub-steps: stably engaging the first engagement portion 25 inside the cavity 7a of the hooking portion 7 of the second module 5, stably engaging the second engagement portion 26 inside the cavity 20a of the hooking portion 20 of the third module 18.
(32) As hereinbefore described, the connecting element 24 can comprise engagement portions 25 distinct and removable from the reinforcing bar; in such arrangement, the step of engaging the connecting element 24 comprises the following sub-steps: inserting the first engagement portion 25 inside the cavity 7a of the hooking portion 7 of the second module 5, filling at least partially the cavity 7a of the hooking portion 7 of the second module 5 with a cementitious material at least partially at a liquid state so that this latter can contact at least part of said first engagement portion 25, constraining, by hardening the cementitious material inside the cavity 7a of the second module 5, said first engagement portion 25, inserting the second engagement portion 26 inside the cavity 20a of the hooking portion 20 of the third module 18, filling at least partially the cavity 20a of the hooking portion 20 of the third module 18 with a cementitious material at least partially at a liquid state so that this latter can contact at least part of said second engagement portion 26, constraining, by hardening the cementitious material inside the cavity 20a of the third module 18, said second engagement portion 26.
(33) After constraining the engagement portions 25, 26 with the modules 5 and 18, the process comprises a step of constraining (fixing) the reinforcing bar to said first and second engagement portions 25 and 26. The process, simultaneously with or after the step of engaging the connecting element 24 with the second and third modules, can comprise at least one step of further fixing the first and second modules which comprises at least the following sub-steps: providing between the reciprocal coupling surfaces of second and third modules, a predetermined quantity of cementitious material at least partially at a liquid state, further constraining, by hardening said cementitious material placed between the reciprocal coupling surfaces, said second and third modules.
(34) Moreover, the process can comprise a step of engaging at least one connecting element 27 (the structure thereof can be identical to the connecting elements 8 and/or 24, for example), on one side, inside the cavity 4a of the hooking portion 4 of the first module 2 and, on the other side, inside the cavity 20a of the hooking portion 20 of the third module 18: the connecting element 27 stably constrains the first module and third modules 2, 18.
3. CEMENTITIOUS COMPOSITION
(35) The present inventors have found that a cementitious composition comprising cement, an inert aggregate, a polymeric fiber, a superfluidifying agent and water, characterized by specific quantities of the components, by the ratio between the water quantity and cement quantity, by the quantity of the superfluidifying agent and by the granulometry of the inert aggregate, is particularly adapted to make structures of reinforced cementitious material by the 3D printing process of the present invention. Particularly, the present inventors, starting from the water/cement ratio necessary to obtain the required mechanical performance and the required setting and hardening kinetics, have optimized the consistency of the mixture by using a fluidifying agent having a specific quantity in relation with the granulometry and capable of absorbing the inert aggregate. Therefore, it is a further aspect of the present invention a cementitious material for making the structure 1 of a reinforced cementitious material according to any one of the attached claims and/or according to the above given description. Therefore, a further aspect of the invention provides a cementitious composition M comprising:
(36) (i) from 15 to 30% by weight of cement with respect to the total weight of the composition,
(37) (ii) from 60 to 80% by weight of at least one inert aggregate, alone or in a mixture with one or more other inert aggregates, with respect to the total weight of the composition,
(38) (iii) from 0.02 to 0.75% by weight of at least one polymeric fiber, alone or in a mixture with one or more other polymeric fibers, with respect to the total weight of the composition,
(39) (iv) from 0.03 to 0.1% by weight of at least one superfluidifying agent, alone or in mixture with one or more other superfluidifying agents, with respect to the total weight of the composition, and
(40) (v) water in a quantity sufficient to reach 100% by weight of the composition, optionally, it can be present:
(41) (vi) from 0.1 to 2.5% by weight of at least one viscosity modifying agent with respect to the total weight of the composition, wherein: the weight ratio between water and cement is comprised between 0.3 and 0.45 or the ratio between water and the equivalent cement is comprised between 0.29 and 0.49; and the maximum diameter of the at least one inert aggregate is less than 12.5 mm.
(42) According to a further aspect of the invention (cementitious composition) a suitable cement is selected among those belonging to the types I, II, III, IV and V, established by the standard EN 197-1, accepted at a national level by the standard UNI EN 197/1. According to a further aspect of the invention, a suitable cement is selected among those belonging to the types I, II, III, IV and V and having strength classes 42,5R and 52,5R according to the standard UNI EN 197/1. Preferably, according to a further aspect of the invention (cementitious composition), a suitable cement is selected among the cements belonging to the classes CEM II/A-L (or A-LL) 42,5R and CEM II/A-L (or A-LL) 52,5R; more preferably selected among the cements belonging to the class CEM II/A-L (or A-LL) 42,5R according to the standard UNI EN 197/1. According to a further aspect of the invention (cementitious composition), said suitable cement has a maximum diameter of the particles less than or equal to 100 microns, preferably less than 50 microns, still more preferably less than 30 microns. According to a further aspect of the invention, the percentage by weight of cement is preferably greater than 18%, more preferably greater than 21%; and/or is preferably less than 27%, more preferably is less than 25%; and/or is preferably comprised between 18% and 27%, more preferably is comprised between 21% and 25% with respect to the total weight of the composition.
(43) Optionally, part of the cement can be substituted with II type additions according to the standard UNI EN 206-1:2006, and particularly with silica fume, or fly ashes, or blast furnace slag, or pozzolana both natural and industrial, comprised between 1 and 3% by weight with respect to the total weight of the composition, preferably silica fume comprised between 1 and 3% by weight with respect to the total weight of the composition; in this case such additions of II type substitute part of the cement by a percentage comprised between 7 and 11% by weight of the cement. In such cases, instead of the “weight ratio between water and cement”, it is considered the “weight ratio between water and equivalent cement” as established by the standard UNI EN 206-1: 2006, according to the following formula:
water/equivalent cement=water/(cement+k×II type addition),
(44) wherein k is a parameter specific according to the type of addition.
(45) Therefore, the water/cement ratio of the cementitious composition of the present invention wherein from 7 to 11% by weight of the cement is substituted with II type additions, is comprised between 0.29 and 0.49. According to the further aspect of the invention, the at least one suitable inert aggregate is selected among fine aggregates, filler and mixtures thereof; preferably the filler is selected in case of I type additions according to the standard UNI EN 12620, more preferably the filler is selected between quartz sand, siliceous sand (microsilica) and calcareous filler (calcium carbonate). Preferably, according to a further aspect of the invention, the composition comprises a mixture of inert aggregates; more preferably comprises sand and quartz sand and/or calcareous filler. According to a further aspect of the invention, said sand is from 90% to 95% and said filler, preferably quartz sand or calcareous filler, is from 5% to 10% with respect to the total weight of the inert aggregates. According to a further aspect of the invention, preferably said sand has a maximum diameter less than 10 mm, still more preferably less than 6 mm, still more preferably less than 4 mm, according to the standard UNI 8520-1 for the compliance, and according to the standard UNI 2332 for determining the granulometric distribution. According to the further aspect of the invention, preferably said filler, preferably quartz sand or calcareous filler, has a maximum diameter less than 0.25 mm, preferably less than 0.125 mm, still more preferably less than 0.063 mm according to the standard UNI 8520-1 for the compliance and according to the standard UNI 2332 for determining the granulometric distribution. According to the further aspect of the invention, the percentage by weight of the at least one inert aggregate, alone or in a mixture with one or more other inert aggregates, is preferably greater than 63%, more preferably greater than 65%, and/or is preferably less than 79%, more preferably is less than 77%; and/or is preferably comprised between 63% and 79%, more preferably is comprised between 65% and 77% with respect to the total weight of the composition.
(46) According to the further aspect of the invention, said at least one polymeric fiber is selected among polyolefinic fibers, preferably polypropylene (PP); polyvinyl alcohol (PVA); polyesters; aliphatic polyamides (Nylon); and mixtures thereof. Preferably, said at least one polymeric fiber is a polypropylene fiber (PP). Preferably, said at least one polymeric fiber, more preferably polypropylene (PP), has a diameter or a maximum size of the cross-section comprised between 0.12 and 0.8 mm, more preferably comprised between 0.25 and 0.35 mm. Preferably, said at least one polymeric fiber, more preferably polypropylene (PP), has a length less than 60 mm, more preferably comprised between 10 and 57 mm, still more preferably between 40 and 55 mm.
(47) According to a further aspect of the invention, the percentage by weight of the at least one polymeric fiber, alone or in a mixture with one or more other polymeric fibers, is preferably greater than 0.025%, more preferably greater than 0.03%; and/or is preferably less than 0.6%, more preferably is less than 0.5%; and/or is preferably comprised between 0.025% and 0.6%, more preferably is comprised between 0.03% and 0.5% with respect to the total weight of the composition. Suitable polymeric fibers can be selected among those commercially available, for example those of the MapeFibre series marketed by Mapei, for example MapeFibre CN54 or NS12; those of the series RUREDIL marketed by RUREDIL, for example RUREDIL X FIBER 19; those of the Polifer series marketed by Polifer, for example Polifer 420. Without wishing to be bound by any explicative theory, the present inventors deem that said polymeric fibers have the function of contributing to the continuity of the flow of said composition exiting the supplying head 101, of providing the not already hardened slurry with tenacity and of decreasing the shrinkage effect of the cementitious composition. According to a further aspect of the invention, said at least one superfluidifying agent is selected among polymers optionally modified polycarboxylic polyethers, naphthalene sulfonic polyethers, polyphosphonics polyethers, acrylic polyethers, and polypropylene glycols, and mixtures thereof. Preferably, said at least one superfluidifying agent is a polymer possibly a modified polycarboxylic polyether.
(48) According to a further aspect of the invention, said at least one fluidifying agent can be present as dust or in a liquid form, for example in an aqueous solution; preferably as dust, said dust has a density comprised between 50 and 80 g/100 cm.sup.3, preferably comprised between 30 and 60 g/100 cm.sup.3. Suitable superfluidifying agents are selected among those commercially available, for example among those of the Melflux® series marketed by BASF, such as for example Melflux® 2651F, and those of the series Dynamon® marketed by Mapei. According to a further aspect of the invention (cementitious composition), the percentage by weight of the at least one superfluidifying agent, alone or in a mixture with one or more other fluidifying agents, is preferably greater than 0.035%; and/or is preferably less than 0.05%; and/or is preferably comprised between 0.035% and 0.05% with respect to the total weight of the composition. According to the further aspect of the invention (cementitious composition), the percentage by mass of the at least one superfluidifying agent, alone or in a mixture with one or more other fluidifying agents, is preferably greater 0.02%, more preferably greater than 0.05%; and/or is preferably less than 0.15%, more preferably is less than 0.10%; and/or is preferably comprised between 0.02% and 0.15%, more preferably is comprised between 0.05% and 0.10% with respect to the total mass of the composition. According to the further aspect of the invention, the percentage by mass of the at least one superfluidifying agent, alone or in a mixture with one or more other fluidifying agents, is preferably greater than 0.1%, more preferably greater than 0.2%, still more preferably greater than 0.25%; and/or less than 0.65%, more preferably less than 0.5%, still more preferably less than 0.40%; and/or is comprised between 0.1% and 0.65%, more preferably is comprised between 0.2% and 0.5%, still more preferably is comprised between 0.25% and 0.40% with respect to the total mass of the cement. Without wishing to be bound by any explicative theory, the present inventors deem that the superfluidifying agent, added with specific quantities at the end of the mixing step in a mixer, adjusts the rheology and thixotropy of the cementitious composition. Particularly, such superfluidifying agent determines a low viscosity during the supplying step by the supplying head 101, for ensuring the printability of the cementitious composition, at the same time determines a high viscosity after the deposition of the composition in order to ensure in this way to separate the layers and support the layers successively deposited by the printing process. Moreover, the present inventors have noted that the superfluidifying dust is better distributed in the mixture and exerts the fluidifying effect in very few minutes after introducing it in the mixer (the effect is visible since it makes homogeneous and “pasty” the mixture). According to a further aspect of the invention, preferably the weight ratio between water and cement is comprised between 0.33 and 0.40. According to the further aspect of the invention, the cementitious composition can optionally comprise: natural or synthetic fibers besides those listed at the point (iii), for example short fibers of hemp, flax, jute; aerating agents, for example the Mapeair AE series marketed by Mapei; lightened inert aggregates having a maximum diameter less than 12.5 mm, such as for example Leca expanded (structural) clays; geopolymeric binders based on metakaolin and an aqueous solution of metal hydroxides (for example sodium hydroxide), such as for example setting accelerators, such as for example the Mapequick series of Mapei; hollow glass nanospheres. In a preferred embodiment, the cementitious composition—according to the further aspect of the present invention—comprises:
(49) (i) from 15 to 30% by weight of cement with respect to the total weight of the composition, selected among those belonging to the types I, II, III, IV and V and having strength classes 42,5R and 52,5R according to the standard UNI EN 197/1;
(50) (ii) from 60 to 80% by weight of at least one inert aggregate, alone or in a mixture with one or more other inert aggregates, with respect to the total weight of the composition, comprising sand and quartz sand or calcareous filler;
(51) (iii) from 0.02 to 0.75% by weight of at least one polymeric fiber, alone or in a mixture with one or more other polymeric fibers, with respect to the total weight of the composition, selected among polyolefinic fibers, preferably polypropylene (PP); polyvinyl alcohol (PVA); polyesters; and aliphatic polyamides (Nylon);
(52) (iv) from 0.03 to 0.1% by weight of at least one superfluidifying agent, alone or in mixture with one or more other superfluidifying agents, with respect to the total weight of the composition, selected among polymers optionally modified polycarboxylic polyethers, naphthalene sulfonic polyethers, polyphosphonics polyethers, and acrylic polyethers.
(53) In a more preferred embodiment, the cementitious composition, according to the further aspect of the present invention, comprises:
(54) (i) from 18 to 27% by weight of cement with respect to the total weight of the composition, selected among those belonging to the types I, II, III, IV and V and having strength classes 42,5R and 52,5R according to the standard UNI EN 197/1;
(55) (ii) from 63 to 79% by weight of at least one inert aggregate, alone or in a mixture with one or more other inert aggregates, with respect to the total weight of the composition, comprising sand and quartz sand or calcareous filler;
(56) (iii) from 0.025 to 0.6% by weight of at least one polymeric fiber, alone or in a mixture with one or more other polymeric fibers, with respect to the total weight of the composition, selected among polyolefinic fibers, preferably polypropylene (PP); polyvinyl alcohol (PVA); polyesters; and aliphatic polyamides (Nylon);
(57) (iv) from 0.035 to 0.05% by weight of at least one superfluidifying agent, alone or in a mixture with one or more other superfluidifying agents, with respect to the total weight of the composition, selected among polymers optionally modified polycarboxylic polyethers, naphthalene sulfonic polyethers, polyphosphonics polyethers, and acrylic polyethers.
(58) In a still more preferred embodiment, the cementitious composition comprises:
(59) (i) from 21 to 25% by weight of cement with respect to the total weight of the composition, selected among those belonging to the types I, II, III, IV and V and having strength classes 42,5R and 52,5R according to the standard UNI EN 197/1;
(60) (ii) from 65 to 77% by weight of at least one inert aggregate, alone or in a mixture with one or more other inert aggregates, with respect to the total weight of the composition, comprising sand and quartz sand;
(61) (iii) from 0.03 to 0.5% by weight of at least one polymeric fiber, alone or in a mixture with one or more other polymeric fibers, with respect to the total weight of the composition, selected among polyolefinic fibers, preferably polypropylene (PP); polyvinyl alcohol (PVA); polyesters; and aliphatic polyamides (Nylon); preferably polypropylene (PP) fibers;
(62) (iv) from 0.035 to 0.05% wt. of at least one superfluidifying agent, alone or in a mixture with one or more other superfluidifying agents, with respect to the total weight of the composition, selected among polymers optionally modified polycarboxylic polyethers, naphthalene sulfonic polyethers, polyphosphonics polyethers, and acrylic polyethers; preferably modified polycarboxylic polyether polymers. As an alternative, the cementitious composition of the invention can be defined based on the quantity expressed by kg of the components from (i) to (v) present in a cubic meter of said composition. The cementitious composition of the invention comprises:
(63) (i) from 300 to 650 kg of cement per cubic meter of the composition,
(64) (ii) from 1,000 to 2,000 kg of at least one inert aggregate per cubic meter of the composition,
(65) (iii) from 0.5 to 2 kg of at least one polymeric fiber per cubic meter of the composition,
(66) (iv) from 0.5 to 2.8 kg of at least one superfluidifying agent per cubic meter of the composition,
(67) (v) from 100 to 200 liters of water per cubic meter of the composition.
(68) The cementitious composition, according to the invention, falls into a consistency class S1. De facto, said composition in a green state, has a value of the Abrams cone slump test (SLUMP), measured according to the standard EN 12350-2:2009, comprised between 10 and 40 mm, preferably comprised between 30 and 40 mm. The cementitious composition according to the invention, hardened after curing for 28 days, has an average cubic strength value R.sub.cm and an average cylindrical strength f.sub.cm, measured according to the standard EN 12390, comprised respectively between 50 and 60 MPa and between 40 and 48 MPa. A further aspect of the present invention comprises a method of preparing the cementitious composition according to the invention, comprising:
(69) a) mixing the at least one inert aggregate (i) with the cement (ii),
(70) b) adding water to the obtained mixture and mixing in order to form a slurry,
(71) c) adding to the obtained slurry the at least one polymeric fiber (iii) and mixing,
(72) d) adding the at least one fluidifying agent (iv) and mixing.
(73) According to a further aspect of the invention (method of preparing the cementitious composition), a suitable cement is selected among those belonging to the types I, II, III, IV and V, established by the standard EN 197-1, accepted at a national level by the standard UNI EN 197/1.
(74) According to a further aspect of the invention, a suitable cement is selected among those belonging to the types I, II, III, IV and V and having strength classes 42,5R and 52,5R according to the standard UNI EN 197/1. Preferably, according to the further aspect of the invention (cementitious composition), a suitable cement is selected among those cements belonging to the classes CEM II/A-L (or A-LL) 42,5R and CEM II/A-L (or A-LL) 52,5R; more preferably selected among the cements belonging to the class CEM II/A-L (or A-LL) 42,5R according to the standard UNI EN 197/1. Said suitable cement has a maximum diameter of the particles less than or equal to 100 microns, preferably less than 50 microns, still more preferably less than 30 microns. According to the method of preparing the composition according to the invention, the at least one suitable inert aggregate is selected among sand, filler and mixtures thereof, preferably the filler is selected in the family of the I-type additives according to the standard UNI EN 12620, more preferably the filler is selected among quartz sand, silica sand (microsilica), and calcareous filler. According to the method of preparing the composition according to the invention, said sand has a maximum diameter less than 12.5 mm, preferably less than 10 mm, still more preferably less than 6 mm, still more preferably less than 4 mm, according to the standard UNI 8520-1 for the compliance and according to the standard UNI 2332 for determining the granulometric distribution. According to the method of preparing the composition according to the invention, said filler, preferably quartz sand or calcareous filler, has a maximum diameter less than 0.25 mm, preferably less than 0.125 mm, still more preferably less than 0.063 mm, according to the standard UNI 8520-1 for the compliance and according to the standard UNI 2332 for determining the granulometric distribution. According to the method of preparing the composition according to the invention, said at least one polymeric fiber is selected among polyolefinic fibers, preferably polypropylene (PP), polyvinyl alcohol (PVA); polyesters; aliphatic polyamides (Nylon); and mixtures thereof. Preferably, said at least one polymeric fiber is a polypropylene (PP) fiber. Preferably, said at least one polymeric fiber, more preferably a polypropylene (PP) fiber, has a diameter or a maximum dimension of the cross-section comprised between 0.12 and 0.8 mm, more preferably comprised between 0.25 and 0.35 mm. Preferably, said at least one polymeric fiber, more preferably polypropylene (PP), has a length less than 60 mm, more preferably comprised between 10 and 57 mm, still more preferably between 40 and 55 mm.
(75) According to the method of preparing the composition in agreement with the invention, said at least one superfluidifying agent is selected among polymers optionally modified polycarboxylic polyethers, naphthalene sulfonic polyethers, polyphosphonic polyethers, acrylic polyethers, polypropylene glycols and mixtures thereof. Preferably, said at least one superfluidifying agent is a polymer possibly a modified polycarboxylic polyether. According to the method of preparing the composition in agreement with the invention, the mixing steps from a) to d) are performed at a speed comprised between 20 and 60 rounds per minute, more preferably between 30 and 50 rounds per minute. According to the method of preparing the composition in agreement with the invention, the mixing step a) and c) is extended for a time comprised between 10 seconds and 10 minutes, preferably between 1 minute and 7 minutes, more preferably between 2 minutes and 5 minutes. According to the method of preparing the composition in agreement with the invention, the mixing step b) is extended for a time comprised between 10 seconds and 10 minutes, preferably between 1 minute and 7 minutes, more preferably between 2 minutes and 5 minutes in which all the quantity of water is added; after adding water, the mixing step is extended for a time comprised between 10 seconds and 15 minutes, preferably between 1 minute and 10 minutes, more preferably between 2 minutes and 7 minutes. According to the method of preparing the composition in agreement with the invention, the mixing step d) is extended for a time comprised from 20 seconds to 20 minutes, preferably between 1 minute and 15 minutes, more preferably between 2 minutes and 13 minutes.
(76) In a further aspect of the present invention, it is provided an use of the cementitious composition according to the invention for 3D printing modules/structures of reinforced cementitious material.
3.1 EXPERIMENTAL SECTION
Example 1
(77) 40 liters of a cementitious composition representative of the invention are prepared. In the step a), about 57.2 kg of sands (maximum diameter: 2 mm) and about 3.98 kg of quartz sand (maximum diameter: 0.125 mm) corresponding respectively to 1,431 kg and 99.5 kg per cubic meter of the final cementitious composition, are introduced into a cylindrical type electric mixer having a maximum capacity of 140 liters, beforehand wetted to saturation. Subsequently, about 19.9 kg of CEM II/A-LL 42.5 R corresponding to 498 kg per cubic meter of the final cementitious composition are added into the mixer, and then the dry powders are mixed for about 3 minutes, at a rotation speed of the mixer of about 40 rounds per minute. In the step b) water is gradually added, for a total of about 7 liters corresponding to 176.5 liters per cubic meter of the final cementitious composition, by mixing for a time corresponding to the addition of all the water quantity, corresponding to about 3 minutes at a rotation speed of the mixer of about 40 rounds per minute; then, the mixing step is extended for about other 5 minutes under the above given same rotation speed conditions of the mixer. In the step 5), polypropylene fibers (MapeFibre CN54, marketed by Mapei) in a quantity of 0.04 kg, corresponding to 1 kg per cubic meter of the final cementitious composition, are added and are mixed for approximately 3 minutes, at a mixer rotation speed of about 40 rounds per minute. In the step d), a quantity of 0.069 kg corresponding to 1.74 kg per cubic meter of the final cementitious composition, of the superfluidifying additive based on a modified polycarboxylic polyether (Melflux® 2651F marketed by BASF) is gradually added (⅓+⅓+⅓), and is mixed for further 5-10 minutes.
Example 2
(78) Determining the consistency class of the cementitious composition prepared as described in the example 1 in a green state, measured according to the standard EN 12350-2:2009. The consistency class was measured by the Abrams cone, consisting of a cone made of galvanized steel or stainless steel having a thickness of about 1.5 mm and having a frustoconical shape with the following internal dimensions: diameter of the lower base: 200±2 mm; diameter of the upper base: 100±2 mm; height: 300±2 mm.
(79) The composition described in the example 1 in a green state (before being inserted in the printer) was quickly introduced and completely packed in the frustoconical container by following the suggestions of the cited standard. Immediately after removing the mould, the slump of the cone S was measured by the difference between the nominal height of the mould (hm=300 mm) and the height of the tallest point of the sample hs, by an approximation to the nearest 10 mm. The slum of the Abrams cone of the cementitious composition of the invention in a green state, was 34 mm, in other words said cementitious composition falls into the consistency class S1.
Example 3
(80) Determining the average cubic strength value R.sub.cm and the average cylindrical strength value f.sub.cm of the cementitious composition prepared as described in the example 1, hardened after maturing for 28 days, measured according to the standard EN 12390. The average cubic strength R.sub.cm and the average cylindrical strength f.sub.cm under an uniaxial compression (by controlling the force) were measured on normalized specimens and therefore respectively on 4 cubic samples having a side of 150 mm and on 4 cylindrical samples having a diameter of 150 mm and a height of 300 mm. The average strength R.sub.cm of the cementitious composition of the invention hardened after curing it for 28 days, is of 53.5 MPa; the average strength f.sub.cm of the hardened cementitious composition itself after curing it for 28 days, is of 44.4 MPa. By the data given in the examples 2 and 3, it was found that the cementitious composition of the present invention in a green state, exhibits an optimal consistency, consequently such cementitious composition exhibits an optimal capacity of being supplied through the supplying head 101 and of remaining separated in layers and supporting the gradually printed layers. Moreover, such hardened cementitious composition has an optimal capacity of opposing to the compression, therefore is capable of compensating possible weaknesses of the connecting points between adjacent layers.
Example 4
(81) Determining the average compression strength value f.sub.cpm of hollow cylindrical construction elements obtained by 3D-printing the cementitious composition prepared as described in the example 1 and hardened after curing it for 28 days. The cementitious composition of the invention was used for preparing three construction elements C1, C2 and C3, by the above described 3D-printing process of the present invention. Such construction elements are hollow cylinders, having a height of 200 mm, and average thickness of the walls of about 50 mm and being formed by 10 layers. The obtained thickness of the walls corresponds to a single layer of the material printed with the above described cementitious composition. The average outer (D.sub.ext, ave) and inner diameters (D.sub.int, ave) measured in mm of the three hollow cylinders, and also the average area (A.sub.ave) of the cross-section measured in mm.sup.2 from these latter, the average area (A.sub.eff) of the effective transversal cross-section measured in mm.sup.2 from the effective width of the transversal cross-section (S.sub.eff, see
(82) TABLE-US-00001 TABLE 1 D.sub.ext.sub., ave D.sub.int, ave A.sub.ave A.sub.eff F.sub.max f.sub.cp f.sub.cpm f.sub.cp.sub.
(83) The average compression strength, if calculated on the average surface of the cross-section (f.sub.cpm) of the three tested construction elements C1, C2 and C3, is 16% less than the average cylindrical strength f.sub.cm of the cementitious composition used for 3D-printing the construction element (37.2 MPa vs 44.4 MPa). The correct calculation performed by considering the effective area of the cross-section, in other words by considering only the net surface in contact with the layers (determined by the segment S_eff shown in the cross-section view of the cylindrical specimen of
Example 5
(84) Determining the flexural rigidity value of a three-dimensional structure obtained by 3D-printing the cementitious composition prepared as described in the example 1.
(85) The cementitious composition of the invention was used for preparing, from a determined 2D profile, a three-dimensional structure (INV) long 3.20 m having an overall rectangular cross-section with a width of 0.20 m and a height of 0.40 m, formed by 7 modules, made by the 3D-printing process of the present invention, as shown in
f=5*ql.sup.4/(384*EI).fwdarw.EI.sub.eq=5*ql.sup.4/(384*f)
(86) wherein the value of the (own) load of the beam q and the length thereof I, and the measure deflection f are known; wherein EI is the flexural rigidity, in other words E represents the Young module of the material, and I represents the moment of inertia of the cross-section.
(87) Table 2 shows the flexural rigidity values EI of the three-dimensional structure of the invention (INV) and of said equivalent solid structure (RIF) when is uncracked (RIF1, the percentage of cracks is less than 50%) and when is cracked (RIF2, the percentage of cracks is greater than 60%).
(88) TABLE-US-00002 TABLE 2 EI Structure N/mm.sup.2 INV 1.20 * 10.sup.13 RIF1 2.6 * 10.sup.13 RIF2 0.13 * 10.sup.13
(89) The flexural rigidity value of the structure of the invention is intermediate between the one of the solid uncracked structure (RIF1) and of the cracked one (RIF2), this latter was evaluated according to the “Norme Tecniche per le Costruzioni (NTC2008)”.
(90) From the data shown in the example 5, it was found that, despite the cavities present in the modules printed according to the process of the invention and the smaller quantities of cementitious material present in the structure of the invention could determine a too high deformability of the structure, the present inventors have surprisingly found that the deformability of such structure amounts to acceptable values. This is an interesting result because enables to better exploit the possibilities of the 3D printing for designing shapes which are, at the same time, structurally efficient and characterized by a low use of cementitious material.
(91) Finally, the cementitious composition of the present invention, characterized by the specific quantity of components from (i) to (v), particularly characterized by the ratio between the water quantity and cement quantity, by the quantity of superfluidifying agents and by the granulometry of the inert aggregates, is particularly suitable for making structures of reinforced cementitious material obtained by the 3D printing process of the present invention.