composite material comprising: a bonding matrix and a filler material incorporated in the bonding ma

专利摘要:
CONNECTION ELEMENT, CONNECTION MATRIX AND COMPOSITE MATERIAL HAVING THE CONNECTION ELEMENT, AND MANUFACTURING METHOD OF THESE. The present invention relates to a connecting element, a connecting element matrix and composite materials with a wide range of attractive properties that can be optimized, including, but not limited to, mechanical properties, thermal properties, magnetic properties, optical properties and nuclear properties, as a result of a first layer and second layer structure or core, first layer structure, and second layer of the connecting elements, as well as methods for manufacturing the connecting elements and the ceramic and / or materials corresponding composites.
公开号:BR112013022658B1
申请号:R112013022658-7
申请日:2012-03-02
公开日:2021-03-09
发明作者:Richard E. Riman；Surojit Gupta；Vahit Atakan；Qinghua Li
申请人:Rutgers, The State University Of New Jersey；
IPC主号:

专利说明:

[001] This order claims priority to U.S. Interim Serial Order Number 61 / 449,659, filed on March 5, 2011, which is incorporated herein by reference. FIELD OF THE INVENTION
[002] The present invention generally relates to ceramic materials and / or composites. More specifically, the present invention relates to ceramic and / or composite materials that comprise bonding elements that improve the mechanical and other properties associated with the ceramic and / or composite materials, as well as methods for making the connecting elements and materials. corresponding ceramic and / or composites. BACKGROUND
[003] Conventional ceramic materials, such as cement, concrete and other similar materials can exhibit properties of weak material. These weak material properties may be due to the fact that the bonds, for example, hydrate bonds, in the material are often weak. Hydrate bonds are bonds that contain water in its molecular form. Hydrated Portland cement is an example of a material that contains hydrate bonds such as CaO ^ 2Siθ2 ^ 4H∑O and CaO ^ H∑O. This weakness can cause the ceramic material to fail prematurely, which is clearly an undesirable feature of the material.
[004] Thus, a need exists to improve the bonds and, more generally, the bonding matrix associated with ceramic materials, such as cement, concrete and other similar materials, in order to provide ceramic materials with improved material properties.
[005] All references cited here in this specification are incorporated by reference in their entirety. SUMMARY OF THE INVENTION
[006] In accordance with exemplary embodiments of the present invention, the connecting elements, connecting dies, composite materials, and methods of manufacturing said connecting elements result in a wide range of attractive properties that can be optimized, including, but not limited to, limited to, mechanical properties, thermal properties, magnetic properties, optical properties and nuclear properties, as a result of the core / first layer / second layer structure of the connecting elements.
[007] Additional features and advantages of the invention will be presented in the description that follows, and in part will be evident from the description, or can be learned by practicing the invention. The objectives and other advantages of the invention will be realized and achieved by the structure particularly pointed out in the description and written claims thereof as well as in the attached drawings.
[008] It should be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to provide further explanation of the invention as claimed. BRIEF DESCRIPTION OF THE DRAWINGS
[009] The attached drawings, which are included to provide an additional understanding of the invention and are incorporated and form a part of this specification, illustrate modalities of the invention and together with the description serve to explain the principles of the invention. In the drawings: - FIGS. 1 (a) to 1 (c) are schematic cross sections of unique connecting elements according to exemplary embodiments of the present invention, illustrating three exemplary core morphologies: (a) fibrous, (b) elliptical, and (c) equiaxial. - FIGS. 2 (a) to 2 (f) are side view and cross-sectional view of composite materials according to exemplary embodiments of the present invention, illustrating (a) fiber-oriented connection elements 1D in a diluted connection matrix (elements connection elements are not touching), (b) 2D-oriented plate-like connection elements in a diluted connection matrix (connection elements are not touching), (c) 3D-oriented plate-like connection elements in a matrix diluted bond (bonding elements are not touching), and (d) nameplate-shaped bonding elements randomly oriented in a diluted bonding matrix (bonding elements are not touching), where the composite materials include the bonding matrix and filler components such as polymers, metals, inorganic particles, aggregates etc., (e) a concentrated bonding matrix (with a fraction in volume sufficient to establish a percolation network) of bonding elements the matrix is 3D oriented, and (f) a concentrated bonding matrix (with a fraction in volume sufficient to establish a percolation network) of randomly oriented connecting elements, in which filler components such as polymers, metals, inorganic particles, aggregates etc. can be included. Structures comprising a mixture of connecting elements that touch each other and others that are dispersed units are also provided for but not shown here. The connecting elements can comprise any of the basic multilayer structures shown in FIG. 1 or may have any additional morphologies, but are shown in an abbreviated form for this figure. Cross sections of representative core particle morphologies are shown for clarity. FIG. 3 illustrates different connectivity patterns in two component composite material systems according to exemplary embodiments of the present invention. Shaded regions show the bond matrix regions, and non-shaded regions are filler components, such as metals, aggregates, inorganic particles or polymers. (FIG. 3 adapted from: R. E. Newnham, D. P. Skinner and L. E. Cross, "Connectivity and piezoelectricpyroelectric composites", Mat. Res. Bull. Vol. 13, pages 525 to 536, 1978). - FIGS. 4 (a) and 4 (b) show in (a) a 3-0 composite material according to exemplary embodiments of the present invention, comprising a bonding matrix and equiaxial filler particles randomly distributed in the bonding matrix, and (b) material composite 3-1 according to exemplary embodiments of the present invention comprising bonding matrix and filler components in the form of oriented fiber. - FIGS 5 (a) and 5 (b) show scanning electron microscopy (SEM) images of (a) secondary electron (SE) and (b) backscattered electron (BSE) of a bonding matrix according to a modality example of the present invention, composed of crystalline volastonite core fibers encapsulated by amorphous silica and surrounded by CaCO3 particles. - FIGS. 6 (a) to 6 (c) show chemical mapping by energy dispersive X-ray spectroscopy (EDS) of a binding matrix according to an exemplary embodiment of the present invention, illustrating the Si overlay map (FIG. 6 ( a)) and Ca (FIG. 6 (b)). In FIG. 6 (c) the regions of CaSiO, SiO2, and CaCO3 are indicated by arrows. Volastonite (CaSiO3) core particles in the form of fiber are encapsulated by regions rich in SiO2 and surrounded by CaCO3 particles. FIG. 7 shows a field emission scanning electron microscopy (FESEM) image of a 20 N Vicker hardness indentation in a P3 bonding matrix (Table 6) according to an embodiment of the present invention. - FIGS. 8 (a) to 8 (c) show FESEM micrographs of (a) an indentation (Image SE), (b) higher magnification of the point marked D in (b) (Image BSE), and (c) a robust interface between the core wollastonite grain and the silica phase coating. FIG. 9 shows a stress versus displacement curve of a P3 connection matrix (see also Table 4) in compression of a mode of the present invention. FIG. 10 shows a stress versus displacement curve of a composite material FB4 (see Table 3) in compression according to an exemplary embodiment of the present invention. - FIGS. 11 (a) to 11 (d) show the interaction of a P3 binding matrix (see also Table 4) with (a) SiO2 and (b) SiO2, (c) Fly ash with high Ca content (HCFA) and (d) CaCO3 according to the modalities of the present invention. Observation of the P3 binding matrix and SiO2 interface (FIGS. 11 (a) and (b)) reveals that CaCO3 particles and a silica-rich coating around the volastonite core fibers formed an interface with silica particles externally added. - FIGS. 12 (a) and 12 (b) illustrate the failure behavior of a composite material 0-3 according to an embodiment of the present invention. FIG. 12 (a) shows the composite 0-3, where 70 %% by volume. of particulate components of sand (silica) are dispersed in the P3 bonding matrix with porosities in the structure (see also Table 4). This composite material showed a gradual failure during compression, and had a compressive strength of ~ 55 MPa (FIG. 12 (b)). - FIGS. 13 (a) to 13 (d) illustrate exemplary embodiments of the present invention having different levels of hierarchical repetition structures. FIGS. 13 (a) and 13 (b) illustrate a level 1 hierarchical system, and FIGS. 13 (c) and 13 (d) illustrate a level 2 hierarchical system. FIGS. 14 (a) to (c) show different optical micrographs of a composite material according to an embodiment of the present invention. FIGS. 14 (a) and 14 (b) show optical micrographs of the composite material formed using a 1: 2: 2 volumetric ratio of FB1 Fiber Cores (Table 3), (300 to 500) μm of sand, and (2 to 4) mm of sand and gravel respectively, and FIG. 14 (c) shows the bonding matrix in the void spaces of sand particles, and a thick layer of bonding matrix surrounded sand particles to also act as a cementation phase. FIG. 15 shows (a) deformation versus temperature, and (b) temperature profile versus FB1B time during thermal cycling between -40 ° C and 100 ° C. FIG. 16 shows a specific heat lot (cp) of P3 (Table 4) as a function of temperature. The experiment was carried out according to ASTM E1269. FIG. 17 shows digital photographs of, (a) conventional natural sandstone and a sandstone mimic according to one embodiment of the present invention, (b) conventional granite and a granite mimic according to one embodiment of the present invention, and (c) terracotta conventional and a terracotta mimic according to an embodiment of the present invention. FIG. 18 shows the effect of the reaction time on, (a) compressive strength, and (b) tensile strength of the bonding matrix (104 ° C and -413.69 kPa (300 psi) of CO2 starting pressure). The bonding matrix and P3 is formed after 20 h of reaction (Table 4). FIG. 19 shows graphs and flexural strength versus displacement of (a) FB1B binding matrix with metal fibers according to one embodiment of the present invention, (b) pristine CPC2 matrix (Curve A) according to one embodiment of the present invention, and CPC2 with 10 %% by weight of metal fibers (curve C, composition FRCPC2, Table 16) and with 2.5 %% by weight of PVA fibers (Curve B) according to the modalities of the present invention, and (c ) comparison of the flexural strength of the FB1B bonding matrix with 10% by weight as received and oxidized (rusty) metal fibers (FRCPC2 and RFRCPC2 compositions, Table 16). FIG. 20 shows images of (a) SE and (b) steel fiber interface BSE a bonding matrix according to a modality of the present invention, and EDS chemical mapping of (c) Ca, (d) Si, (e ) Fe, and (f) O. - FIG. 21 shows the SE FESEM microstructure of the SRC3 composite material (see also Table 18) according to an embodiment of the present invention. FIG. 22 shows (a) a batch of flexural stress versus displacement of an FSRBC1 composite material (see also Table 19), and (b) a digital photograph, which shows the flexion of the FSRBC1 composite material during testing on an INSTRON system. FIG. 23 shows FESEM, images of (a) SE and (b) BSE of the carbonated olivine microstructure according to one embodiment of the present invention, and at higher magnifications, images of (c) BSE, (d) SE, and (c ) BSE from carbonated olivine particles of different morphologies. FIG. 24 shows FESEM, images of (a) SE and (b) BSE of the carbonated diopside microstructure according to one embodiment of the present invention, and at higher magnifications, images of (c) SE and, (d) BSE of particles of carbonated diopside. DETAILED DESCRIPTION OF THE MODALITIES ILLUSTRATED MODALITIES
[010] Reference will now be made in detail to an embodiment of the present invention, the example of which is illustrated in the accompanying drawings. Connecting element
[011] FIGS. 1 (a) to 1 (c) illustrate the cross section of exemplary connecting elements that can comprise at least a portion of a ceramic material or a larger composite. As shown in FIGS. 1 (a) to 1 (c), a given connecting element includes a core, represented by the black inner portion; a first layer, represented by the white intermediate portion; and a secondary or encapsulating layer, represented by the outer portion.
[012] According to the exemplary embodiments of the present invention, a connecting element can exhibit any size and morphology (i.e., shape) depending on the intended application. Table 1 provides a non-exclusive list of possible morphologies. The first layer can include only one layer or multiple sublayers depending on the chemistry of the bonding element and can completely cover the core or partially cover the core. The first layer can exist in a crystalline phase, an amorphous phase or a combination of these. The second layer can include only one layer or multiple sublayers and can also cover the first layer completely or partially. The second layer can also comprise a plurality of particles or it can be of a continuous phase, with minimal observable separate particles. TABLE 1 Regular Geometries (Symmetric Solids)
[013] Polyhedra are solids made of flat surfaces. Each surface is a polygon. For example, Platonic solids, Prisms, Pyramids Non-polyhedra are solids having a curved surface or a mixture of curved and flat surfaces. For example, Sphere, Torus, Cylinder, Cone


Hollow Structures: Geometric Solids with a Cavity in the Center
Other Qualitative Powder Morphology Descriptors (mainly for Irregular Solids)



[014] A connecting element is produced through a transformation process. This process will be described in more detail below. In general, however, the process involves the transformation of reactive precursor particles. The precursor particles may be of any desired size and shape and may be similar in size and shape, or they may vary. The transformation of a given precursor particle will result in a corresponding linker having a similar size and shape. The transformation process proceeds by exposing the precursor particles to a reactive liquid. A reagent associated with the liquid then reacts with the chemical elements that make up the precursor particles, and more specifically, the chemical elements in the peripheral portion of the precursor particles. This reaction eventually results in the formation of the first and second layers mentioned above.
[015] In a first embodiment of the bonding element described above, the precursor particles comprise two or more chemical elements, such as a ceramic material comprising multiple cations or a metallic material comprising multiple metals. During the transformation process, the reagent in the liquid preferably reacts with at least one first of the chemical elements, where the reaction between the reagent and the at least one first chemical element results in the formation of the first and second layers, the first layer comprising a derived from the precursor particle, generally excluding the at least one first chemical element, whereas the second layer comprises a combination of the reagent and the at least one first chemical element. In comparison, the nucleus comprises the same or almost the same chemical composition as the precursor particle. For example, peripheral portions of the nucleus may vary from the chemical composition of the precursor particle due to the selective leaching of particular chemical elements from the nucleus.
[016] Thus, the nucleus and the second layer share at least one first chemical element of the precursor particle, and the nucleus and the first layer share at least one other chemical element of the precursor particle. The at least one first chemical element shared by the core and the second layer can be, for example, at least one alkaline earth element (beryllium, magnesium, calcium, strontium, barium and radium). The at least one other chemical element shared by the core and the first layer can be, for example, silicon, titanium, aluminum, phosphorus, vanadium, tungsten, molybdenum, gallium, manganese, zirconium, germanium, copper, niobium, cobalt, lead , iron, indium, arsenic and / or tantalum.
[017] In a second exemplary embodiment, the precursor particles may comprise two or more chemical elements; however, during the transformation process, the reagent in the liquid preferably reacts with at least one of the first chemical elements, in which the reaction between the reagent and the at least one first chemical element results in the formation of the first and second layers, the first layer and the second layer both comprising a combination of the reagent and the at least one first chemical element. Thus, the cations associated with the chemical composition of the first layer correspond to a first of the two or more chemical elements of the precursor particles, and the cations associated with the second layer also correspond to the first of the two or more chemical elements of the precursor particles.
[018] Still in an exemplary alternative mode, the reaction between the reagent and at least one first chemical element of the precursor particles can be carried out for completion thus resulting in the first layer becoming the nucleus of the binding element and having a composition chemistry that is different from that of the precursor particles, and at least one additional or secondary shell layer comprising a composition that may or may not include at least one first chemical element of the two or more chemical elements of the precursor particles.
[019] The precursor particles can be selected from any suitable material that can undergo the transformation described above. For example, precursor particles can include oxides and non-oxides of silicon, titanium, aluminum, phosphorus, vanadium, tungsten, molybdenum, gallium, manganese, zirconium, germanium, copper, niobium, cobalt, lead, iron, indium, arsenic, tantalum , and / or alkaline earth elements (beryllium, magnesium, calcium, strontium, barium and radium). For example, the precursor particle may include oxides such as silicates, titanates, aluminates, phosphates, vanadates, tungstates, molybdates, gallates, manganates, zirconates, germinates, cuprates, stannates, hafnates, chromates, niobates, cobaltates, plumbates, ferrites , arsenates, tantalates and combinations thereof. In a preferred embodiment, the precursor particles include silicates such as orthosilicates, serosilicates, cyclosilicates, inosilicates, phyllosilicates, tectosilicates and / or hydrated calcium silicate. It is believed that the various specific silicates listed in Table 2A can be used as the precursor particle. It is also believed that several specific non-silicates listed in Table 2A can be used as the precursor particle and that the various rock-containing materials as listed in Table 2A can be used as the precursor particle. Table 2A: List of reactive precursors 1. Silicates






[020] It is also believed that some residual materials can be used as the precursor particles. Waste materials can include, for example, minerals, industrial waste, or an industrial chemical material. Exemplary waste materials include mineral silicate, iron ore, periclase, gypsum, iron (II) hydroxide, fly ash, bottom ash, slag, glass, oily shells, red mud, battery waste, recycled concrete, mining waste , paper ash, or salts from the concentrated reverse osmosis brine.
[021] Additional precursor particles may include different types of rock-containing materials such as lime-silicate rock, fitch formation, hebron gneiss, layered gneiss, intermediate limb, claystone, quartzite, intermediate, dark precambrian sediments , feldspar quartzite with smaller limestone beds, high grade metasedimentary shale biotite, biotite gneiss, shale mica, quartzite, hoosac formation, partridge formation, Washington gneiss, Devonian formation, greenvale inlet siluriana, ocoee supergroup , metaarenite, metagrauvaca, Rangeley formation, amphibolites, calcitic and dolomite marble, manhattan formation, faded and gray biotite-quartz-feldspar gneiss, and waterford group.
[022] Precursor particles can also include igneous rocks such as, but not limited to, andesite, anorthosite, basinite, boninite, carbonatite and charnoquite, sedimentary materials such as, but not limited to, claystone, arcosis, breches, cataclasite, chalk, clayey stone, horny flint, flint, gitsone, lighine, limestone, slime shale, sandstone, shale, and siltstone, metamorphic materials such as, but not limited to, amphibolites, epidiorite, gneiss, granulite, green, corneal, marble, pelite, phyllite, quartzite, shale, skarn, slate, talcum carbonate, and soapstone, and other varieties of rocks such as, but not limited to, adamelite, apinite, afanites, borolanite, blue granite, epidosite, phellites, flint , gangster, ijolite, jadeitite, jasproid, kenyite, vogesite, larvikite, litchfieldite, luxullianite, mangerite, minette, novaculite, pyrolite, rapakivi, porphyroid, shonkinite, taconite, teschenite, teralite, and variolite.
[023] Likewise, the first layer can comprise any chemical composition that can be derived from the chemical compositions of the various precursor materials described above.
[024] As explained previously, the secondary, encapsulating layer can comprise a combination of the reagent and the at least one chemical element of the precursor particle. According to exemplary embodiments of the present invention, the secondary or encapsulating layer can comprise several possible chemicals. For example, the encapsulating layer may comprise a carbonate having a naturally occurring structure. The secondary or encapsulating layer can also comprise other possible carbonate chemicals, as well as sulfates, phosphates and other anionic compounds capable of dissolving in a solvent and reacting with a precursor particle.
[025] Table 2B provides exemplary modalities of different types of chemicals for the first and second layers that can be obtained when using different precursor materials. The examples listed in Table 2B are not intended as limiting or as an exhaustive list of possible materials but only as exemplary as many additional different types of chemicals can be obtained depending on the precursor material. With respect to the first layer, using different precursor materials, silica, alumina or titania can be obtained. The second layer can also be modified by selecting the precursor material. For example, the non-exhaustive list of materials for the second layer exemplified in Table 2B can include various types of carbonates such as, but not limited to, pure carbonates, multiple cation carbonates, carbonates with water or an OH group, layered carbonates with water or an OH group, anion-containing carbonates, silicate-containing carbonates, and carbonate-bearing minerals. Table 2B: Concept that shows how different raw materials (precursors) can be used to generate different types of encapsulating layers


[026] To further provide guidance on how to obtain the exemplary modalities listed above in Table 2B, the following is a more detailed debate on how to obtain some of these exemplary materials.
[027] Referring again to FIGS. 1 (a) to 1 (c), three exemplary, different morphologies for the connecting elements are illustrated. The shape or morphology associated with the core and / or the connecting element can be the same or similar to the shape of the precursor particle. Thus, the precursor particle and, consequently, the corresponding connecting element and / or nucleus can assume any one of several morphologies, including, but not limited to a spherical shape, an elliptical shape, a polygonal shape, such as a hexagon, or any of several other ways. In addition, the morphology of the precursor particle and, consequently, of the corresponding connecting element and / or core can be equiaxial or have a longer axis than the other, as in the case of a wire shape or a rod shape. Furthermore, the precursor particle can comprise a crystal (i.e., "single crystalline") or a plurality of crystals (i.e., "polycrystalline"). The precursor particle may actually comprise a plurality of particles or include an amorphous phase.
[028] In a first specific example, a precursor particle formed predominantly of volastonite, CaSiO3, reacts with carbon dioxide dissolved in water. Calcium cations are believed to be leached from volastonite and thereby change the peripheral portion of the nucleus from volastonite into calcium-deficient volastonite. As calcium cations continue to be leached from the peripheral portion of the nucleus, the structure of the peripheral portion eventually becomes unstable and breaks down, thereby transforming the peripheral calcium deficient volastonite portion of the nucleus into a predominantly silica-rich first layer. However, it is believed that a second layer predominantly of calcium carbonate precipitates out of the water. More specifically, the first layer and the second layer can be formed from the precursor particle according to the following reaction: H2O + CaSiO3 + CO2 = CaCO3 + SiO2 + H2O
[029] The reactive liquid reagent, here carbon dioxide, preferably reacts with the Ca cations of the precursor core of volastonite, thereby transforming the peripheral portion of the precursor core into a first layer rich in silica and a second layer rich in carbonate of calcium. Also, the presence of the first and second layers in the core acts as a barrier for further reaction between volastonite and carbon dioxide, thus resulting in the connecting element having the core, first layer and second layer.
[030] In this and other examples of the first modality, both anions and cations vary in the respective layers. In this example, the core has Ca + 2, Si + 4 and O2- ions, the second layer mainly has Si + 4 and O2- and a small amount of Ca2 + ions, while the second layer has Ca2 + and CO32- ions.
[031] In a second example of the first modality, a precursor particle formed predominantly of forsterite, Mg2SiO4, reacts with dissolved carbon dioxide transforming a peripheral portion of the forsterite into a first layer predominantly of silica and a second layer predominantly of magnesium carbonate. More specifically, the first layer and the second layer can be formed from the precursor particle according to the following reaction: H2O + MgxSiyOz + CO2 = xMgCO3 + ySiO2 + H2O
[032] The reactive liquid reagent, here carbon dioxide, preferably reacts with the Mg cations of the forsterite precursor core, thereby transforming the peripheral portion of the precursor particle into a first layer rich in silica and a second layer rich in carbonate magnesium. Also, the presence of the first and second layers in the core acts as a barrier for further reaction between forsterite and carbon dioxide, thus resulting in the connecting element having the core, first layer and second layer.
[033] In a third example of the first modality, a precursor particle formed predominantly of talc, Mg3Si4O10 (OH) 2, is preheated to 900 ° C for 12 hours, to form dehydrated talc, reacts with dissolved carbon dioxide transforming a peripheral portion of talc in a first layer predominantly of silica and a second layer formed predominantly of MgCO3 ^ xH2O (x = 1-5). More specifically, the first layer and the second layer can be formed from the precursor particle according to the following reaction: H2O + Mg3SÍ4Oio (OH) 2 + CO2 = MgCO3 ^ xH2O (x = 1-5) + SiO2 + H2O
[034] The reactive liquid reagent, here carbon dioxide, preferably reacts with the Mg cations of the talc, thereby transforming the peripheral portion of the precursor particle into a first layer rich in silica and a second layer rich in MgCO3 ^ xH2O ( x = 1-5). Also, the presence of the first and second layers in the core acts as a barrier for further reaction between talc and carbon dioxide, thus resulting in the connecting element having the core, first layer and second layer.
[035] In a fourth example of the first modality, a precursor particle formed predominantly of diopside, MgCaSi2O6, reacts with dissolved carbon dioxide transforming a peripheral portion of the diopside into a first layer predominantly of silica and a second layer formed predominantly of a mixture of carbonate calcium, CaCO3, and magnesium carbonate, MgCO3 and / or dolomite (Mg, Ca) CO3 with varying ratio of Mg and Ca. The second layer can include, for example, a first magnesium carbonate sublayer and a second sublayer of calcium carbonate. Alternatively, the second layer can include a plurality of carbonated particles, such as CaCO3 (Mg, Ca) CO3 and MgCO3.
[036] The first layer and the second layer can be formed from the precursor particle according to one or a combination of both of the following reactions: H2O + MgCaSi2O6 + CO2 = MgCO3 + CaCO3 + SiO2 + H2O H2O + MgCaSi2O6 + CO2 = 2 (Mgx, Cay) CO3 + SiO2 + H2O
[037] The reactive liquid reagent, here carbon dioxide, preferably reacts with the Ca and Mg cations of the diopside, thereby transforming the peripheral portion of the precursor particle into a first layer rich in silica and a second layer rich with a mixture of calcium carbonate and magnesium carbonate and / or dolomite with varying ratio of Mg and Ca. Also, the presence of the first and second layers in the nucleus acts as a barrier for further reaction between diopside and carbon dioxide, thus resulting in the element of connection having the core, first layer and second layer.
[038] In a fifth example of the first modality, the precursor particle / core must be formed of glaucophanium, Na2Mg3Al2Si8O22 (OH) 2, the first layer is rich in alumina and / or silica, and the second layer is MgCO3 and / or NaAlCO3 (OH) 2.
[039] In a sixth example of the first modality, the precursor particle / nucleus is formed from a paligorsque, (Mg, Al) 2S4Ow (OH> 4 (H2O), the first layer is rich in alumina and / or silica, and the second layer is Mg6Al2CO3 (OH) 16.4H2O.
[040] In a seventh example of the first modality, the precursor particle / core is formed of meionite, Ca4 (Al2Si2O8) 3 (Cl2CO3, SO4), the first layer is rich in alumina and / or silica, and the second layer is Ca2SO4CO3 ^ 4H2O.
[041] In an eighth example of the first modality, the precursor particle / core is formed from tanzanite, Ca2Al3O (SiO4) (Si2O7) (OH), the first layer is rich in alumina and / or silica, and the second layer is Ca5Si2O8CO3 , Ca5Si2O8CO3 and / or Ca∑SteOisCOs ^ H∑O.
[042] In a ninth example of the first modality, the precursor particle / nucleus is formed from (Ba0,6Sr0,3Ca0,1) TiO3, the first layer is rich in titania, and the second layer is olekminskita Sr (Sr, Ca, Ba) (CO3) 2.
[043] As shown in Table 2C, the second layer can also be modified by introducing anions and / or cations in addition to the CO3-2 anions already present. Consequently, the second layer may comprise a chemical composition including cations bound with anions corresponding to one or more reagents. The cations associated with the chemical composition of the second layer can be attached to the anions of a first reagent. The cations associated with the chemical composition of the second layer can be attached to the anion of a reagent except the first reagent. The cations associated with the chemical composition of the second layer can alternatively be attached to the anions of a first reagent and to the anions of a second or more reagents. Such additional anions and cations can be used to modify the second layer to increase its physical and chemical properties such as flame resistance or acid resistance. For example, as shown in Table 2C, although the first layer is maintained as a silica-rich layer, the second layer can be modified by adding extra anions or cations to the reaction. Some exemplary anions that can be added include PO4-2 and SO4-2. Other anions or cations can also be used. As shown in Table 2C, the final results can include, for example, different carbonates that carry phosphate, sulfate, fluoride or combinations thereof. As in Table 2B, the examples provided in Table 2C are exemplary only and should not be intended as limiting as they are not an exhaustive list of possibilities. Table 2C: Concept that shows how to use volastonite as a core particle, as a different source of anions and / or cations, in addition to CO3-2 anions, can be used to generate modified encapsulating layers

[044] In another exemplary embodiment, a precursor particle can be formed predominantly of copper and can be reacted with water by transforming a peripheral portion of the precursor particle into a first layer formed predominantly of copper hydroxide. Then, carbon dioxide can be used to transform a peripheral portion of the first layer into a second layer predominantly of copper carbonate. The presence of the second layer in the first layer acts as a barrier for further reaction between carbon dioxide and copper, thus resulting in the connecting element having the core, first layer and second layer. In this example, elemental copper is in the core, and the combination of Cu2 + and OH- to form copper hydroxide constitutes the first layer, and the combination of Cu2 + and CO32- to form copper carbonate constitutes the second layer.
[045] A similar result can also be obtained in a modified exemplary mode in which the precursor particle can be formed predominantly of copper oxide. The precursor particle is then reacted with water by transforming a peripheral portion of the precursor particle into a first layer formed predominantly of copper hydroxide. Then, carbon dioxide can be used to transform a peripheral portion of the first layer into a second layer predominantly of copper carbonate. The presence of the second layer in the first layer acts as a barrier for further reaction between carbon dioxide and copper, thus resulting in the connecting element having the core, first layer and second layer. In this modified example, copper is also present in the core, the combination of Cu2 + and OH- in copper hydroxide constitutes the first layer, and the combination of Cu2 + and CO32- in copper carbonate constitutes the second layer. Thus, in these exemplary modalities, the nucleus and the first and second layers all have the same cationic species, but different anions.
[046] In another exemplary embodiment, a precursor particle formed predominantly of bronze reacts with water, transforming a peripheral portion of the precursor particle into a first layer including copper hydroxide. Then, carbon dioxide transforms a peripheral portion of the first layer into a second layer including copper carbonate. The presence of the second layer in the first layer acts as a barrier for further reaction between carbon dioxide and bronze, thus resulting in the connecting element having the core, first layer and second layer.
[047] In yet another exemplary embodiment, a precursor particle can also be formed from a material except copper or bronze. The precursor material can be selected from the previously discussed list. For example, the precursor material may comprise silicon. The precursor may alternatively comprise aluminum. The precursor material may otherwise comprise iron. The precursor could then react to form a hydroxide as the first layer. Thus, for example, the first layer can be formed from a silicon hydroxide. Alternatively, the first layer can comprise an aluminum hydroxide. The first layer on the contrary, could comprise an iron hydroxide. In addition, instead of a hydroxide, the first layer may comprise an oxide. For example, the first layer can comprise a silicon oxide. Alternatively, the first layer can comprise aluminum oxide. In yet another alternative, the first layer may comprise an iron oxide. Similarly, the second layer may constitute a carbonate as discussed above. Thus, for example, the second layer may comprise silicon carbonate. Alternatively, the second layer can comprise aluminum carbonate. In yet another embodiment, the second layer may comprise iron carbonate. As discussed above, other precursor materials can be used, so these core, first layer, and second layer compositions are simply exemplary and should not be intended as limiting. Formation process of the connecting elements
[048] The connection elements described above can be formed, for example, by a gas-assisted hydrothermal liquid phase sintering method. In this method, a porous solid body including a plurality of precursor particles is exposed to a solvent, which partially saturates the pores of the porous solid body, meaning that the pore volume is partially filled with water.
[049] In some systems such as carbonate forming units, completely filling the pores with water is believed to be undesirable because the reactive gas is unable to diffuse from the outer surface of the porous solid body to all internal pores by gaseous diffusion. In contrast, the reactive gas reagent would dissolve in the liquid and diffuse into the liquid phase from the external surface to the internal pores, which is much slower. Liquid phase diffusion may be suitable for transforming thin porous solid bodies, but would be unsuitable for thicker porous solid bodies.
[050] A gas containing a reagent is introduced into the partially saturated pores of the porous solid and the reagent is dissolved by the solvent. The dissolved reagent then reacts with at least the first chemical element in the precursor particle to transform the peripheral portion of the precursor particle into the first layer and the second layer. As a result of the reaction, the dissolved reagent is removed from the solvent. However, the gas containing the reagent continues to be introduced into the partially saturated pores to provide additional reagent to the solvent.
[051] As the reaction between the reagent and the at least first chemical element of the precursor particles progresses, the peripheral portion of the precursor particle is transformed into the first layer and the second layer. The presence of the first layer on the periphery of the nucleus eventually prevents the further reaction by separating the reagent and at least the first chemical element from the precursor particle, thereby causing the reaction to effectively stop, leaving a binding element having the nucleus as the unreacted center of the precursor particle, the first layer on a periphery of the nucleus and a second layer on the first layer.
[052] As a result of the transformation, the nucleus has the same or similar shape as the precursor particle, but smaller in size, the first layer and the second layer can all have uniform or non-uniform thickness that partially or completely cover the nucleus and they can be porous layer depending on the size and shape of the pores that surrounded the precursor particle during the transformation process. The resulting connecting element comprising the core, the first layer and the second layer, is generally larger in size than the precursor particle, filling in the adjacent porous regions of the porous solid body and possibly bonding with adjacent materials in the porous solid body. As a result, the formation of products in liquid form can be formed which are substantially the same size and shape as, but have a higher density than, the porous solid. This is an advantage over traditional sintering processes that cause reduced mass transport to produce a material with a higher density than the original compact.
[053] Without being limited by theory, the transformation of the precursor nucleus can be carried out because at least one first chemical element is leached out of the precursor particle in the solvent, leaving a suppression zone, which generally excludes the first chemical element except for one finite concentration that forms the first layer. The first leached chemical element is then combined with the solvent reagent to form the second layer. The presence of the first and second layers on the periphery of the precursor nucleus eventually prevents further reaction by separating the introduced reagent and the first chemical element from the precursor particle, thereby limiting the reaction to a very slow reaction rate that can be stopped for practice , leaving a connecting element having the core, the first layer on a periphery of the core and a second layer on the first layer. Another theory is that the multiple chemical elements of the precursor particle are dissolved in the solvent and a first chemical element is precipitated to form the first layer and then remaining cations are precipitated to form the second layer.
[054] In an example of the gas-assisted hydrothermal liquid phase sintering method, a porous solid body comprising a plurality of precursor particles is placed in an autoclave chamber and heated. Water as a solvent is introduced into the pores of the porous solid body by evaporating the water in the chamber. A cooling plate above the porous solid body condenses evaporated water which then drips onto the porous body and into the pore of the porous solid body, thus partially saturating the pores of the porous solid body. However, the method of introducing water in this example is one of several ways that water can be released. In another example, the water can be heated and sprayed.
[055] However, carbon dioxide as a reagent is pumped into the chamber, and carbon dioxide diffuses into the partially saturated pores of the porous body. Once in the pores, the carbon dioxide dissolves in the water, thus allowing the reaction between the precursor particles and the carbon dioxide to transform the peripheral portions of the precursor particles into the first and second layers.
[056] In a second embodiment, the precursor particle comprises one or more chemical elements, such as a ceramic material or a metallic material. During the transformation process, a first reagent associated with the liquid reacts with at least one first chemical element in the ceramic or metallic material to form the first layer. A second reagent associated with the liquid then reacts with the first chemical element in a peripheral portion of the first layer to form the secondary, encapsulating layer. Consequently, the core comprises the same chemical composition as the precursor particle, including the first chemical element. The first layer comprises a compound that is a combination of the first reagent and the first chemical element. The second layer comprises a compound that is a combination of the second reagent and the first chemical element.
[057] Without being limited by the method of manufacture, the connection element described above can be formed by exposing the porous solid body including at least one precursor particle, such as copper, to a first reagent, such as water, to form the first layer by reaction of water and copper. Subsequently, a gas-assisted hydrothermal liquid phase sintering method can be performed. In this method, the core and the first layer are exposed to a solvent (such as water), which may or may not initially have a second reagent dissolved in them that reacts with the precursor particle. However, a gas containing additional amounts of the second reagent is introduced into the porous solid structure, thereby supplying the second reagent to the solvent for further reaction with the precursor particle.
[058] As the reaction between the second reagent and the first layer progresses, the second reagent continues to react with the first layer, transforming the peripheral portion of the first layer into the second layer. The formation of the second layer can be by exo-solution of a component in the first layer, and such a second layer can be a gradient layer, in which the concentration of one of the chemical elements (cations) that make up the second layer varies from high to low as the movement of the surface of the core particle towards the end of the first layer. It is also possible that the second layer may also be a gradient composition, such as when the layers are amorphous or composed of solid solutions that have constant or varied compositions.
[059] The presence of the second layer on the periphery of the precursor nucleus eventually prevents the further reaction by separating the second reagent and the first layer, causing the reaction to effectively stop, leaving a connecting element having the nucleus, the first layer in a periphery of the core and a second layer in the first layer. The resulting linker is generally larger in size than the original precursor particle, thereby filling in the adjacent porous regions of the porous solid body and bonding with adjacent materials of the porous solid body. As a result, the method takes into account the formation of products in liquid form having substantially the same shape but with a higher density than the original porous solid. This is an advantage over traditional sintering processes that cause a reduction in mass transport to produce a higher density material than the initial compact. Connection matrix
[060] The connection matrix, according to exemplary embodiments of the present invention, comprises a plurality of connection elements, as previously defined. The bonding matrix can be porous. As explained above, the degree of porosity depends on several variables that can be used to control porosity, such as temperature, reactor design, the precursor material and the amount of liquid that is introduced during the transformation process. Thus, depending on the intended application, the porosity can be adjusted to almost any degree of porosity from about 1 %% by volume to about 99 %% by volume. Composite material
[061] The bonding matrix can incorporate the filler material, which would be mixed with the precursor material during the transformation process described above, to generate a composite material.
[062] In general, the filler material can include any of several types of materials that can be incorporated into the bonding matrix, such as, for example, an inert material and an active material. The inert material is a material that does not undergo any chemical reaction during the transformation and does not act as a nucleation site. The active material can consist of a first type that does not undergo any chemical reaction during the transformation, but acts as a nucleation site and / or a second type that chemically reacts with the bonding matrix during the transformation.
[063] As explained above, the inert material does not undergo any chemical reaction during transformation and does not act as a nucleation site, although it can interact physically or mechanically with the bonding matrix. The inert material can involve polymers, metals, inorganic particles, aggregates, and the like. Specific examples may include, but are not limited to, basalt, granite, recycled PVC, rubber, metal particles, alumina particle, zirconia particles, carbon particles, carpet particles, KevlarTM particles and combinations thereof.
[064] As explained above, the first type of active material does not undergo any chemical reaction during transformation, but acts as a nucleation site. In addition, it can physically or mechanically interact with the binding matrix. For example, when using a bonding element that has a carbonate phase as the second layer, this type of active material can include, for example, limestone, marble powders and other materials containing calcium carbonate.
[065] As explained above, the second type of chemically active material reacts with the bonding matrix during transformation. For example, magnesium hydroxide can be used as a filler and can react chemically with a dissolving calcium component phase from the bonding matrix to form magnesium and calcium carbonate.
[066] More will be said about the use of filler material in combination with the bonding matrix, and how the addition of the filler material can further improve the function, that is, material properties, of the resulting composite material.
[067] The bonding matrix can occupy almost any percentage of the resulting composite material. Thus, for example, the bonding matrix can occupy from about 1% by volume to about 99% by volume of the composite material. Consequently, the volume fraction of the binding matrix can be less than or equal to about 90 %% by volume, such as 70 %% by volume, such as 50 %% by volume, such as 40 %% by volume, such as 30 %% by volume, such as 20 %% by volume, such as less than or equal to about 10 %% by volume. A preferred range for the volume fraction of the binding matrix is about 8 %% by volume to about 99 %% by volume, the most preferred range from about 8 %% by volume to 30 %% by volume.
[068] The composite material, including the bonding matrix and filler, can also be porous. As explained above, the degree of porosity depends on several variables that can be used to control porosity, such as temperature, reactor design, the precursor material, the amount of liquid that is introduced during the transformation process and whether any filler is used. Thus, depending on the intended application, the porosity can be adjusted to almost any degree of porosity from about 1 %% by volume to about 99 %% by volume. For example, the porosity can be less than or equal to about 90 %% by volume, such as 70 %% by volume, such as 50 %% by volume, such as 40 %% by volume, such as 30 %% by volume, such as 20 %% by volume, such as less than or equal to about 10 %% by volume. A preferred range of porosity for the composite material is about 1 %% by volume to about 70 %% by volume, most preferably between about 1 %% by volume and about 10 %% by volume for high density and durability. and between about 50 %% by volume and about 70 %% by volume for light weight and low thermal conductivity. Connection Matrix Orientation
[069] Within the connection matrix, the connection elements can be positioned, in relation to each other, in any of the various orientations. As such, the binding matrix can display any one of several different patterns. For example, connecting elements can be oriented in one direction (that is, a “1-D” orientation), in two directions (that is, a “2-D” orientation) or three directions (that is, an orientation “3-D”). Alternatively, the connecting elements can be oriented in a random pattern (that is, a “random” orientation).
[070] The orientation of the aforementioned and other connection element can be obtained by any of several processes. These processes including, are not limited to, tape casting, extrusion, magnetic field casting and electric field. However, it will be understood that preforming the precursor according to any of these methods would occur before transforming the precursor particle according to the transformation method described above. A person of ordinary skill would understand how to guide the connecting elements.
[071] In addition, the concentration of binding elements in the binding matrix may vary. For example, the concentration of the connecting elements on a volume basis can be relatively high, in which at least some of the connecting elements are in contact with each other. This situation can arise if filling material is incorporated into the connection matrix, but the type of filling material and / or the amount of filling material is such that the level of volumetric dilution of the connection element is relatively low. In another example, the concentration of connecting elements on a volume basis may be relatively low, where the connecting elements are more widely dispersed within the connecting matrix such that few, if any, of the connecting elements are in contact with each other. This situation can arise if the filler material is incorporated in the connection matrix, and the type of filler material and / or the amount of filler material are such that the level of dilution is relatively high. Furthermore, the concentration of the connecting elements on a volume basis may be such that all or almost all of the connecting elements are in contact with each other. In this situation, no filler material may have been added, or if the filler material has been added, the type of filler material and / or the amount of filler material is such that the level of volumetric dilution is almost non-existent.
[072] FIGS. 2 (a) to 2 (d) illustrate a bonding matrix that includes bonding elements in the form of fiber or platelet in different orientations possibly diluted by the incorporation of the filler material, as represented by the spacing between the bonding elements. FIG. 2 (a), for example, illustrates a connection matrix that includes fiber-like connecting elements aligned in a 1-D orientation, for example, aligned with respect to the x direction. FIG. 2 (b) illustrates a connection matrix that includes nameplate-shaped connecting elements aligned in a 2D orientation, for example, aligned with respect to the x and y directions. FIG. 2 (c) illustrates a connection matrix that includes nameplate-shaped connecting elements aligned in a 3-D orientation, for example, aligned with respect to the x, y and z directions. FIG. 2 (d) illustrates a connection matrix which includes connection elements in the form of a nameplate in a random orientation, in which the connection elements are not aligned with respect to any particular direction.
[073] FIGS. 2 (e) and 2 (f) illustrate a connection matrix that includes connection elements in the form of a platelet in two different orientations and concentrations. FIG. 2 (e), for example, illustrates a connection matrix that includes a relatively high concentration of platelet-shaped connection elements that are aligned in a 3-D orientation, for example, aligned with respect to the x, y and z directions. The relatively high concentration of the connection element is illustrated by the lack of filler material around the connection elements; thus, there is little to no dilution of the connecting elements. In contrast, FIG. 2 (f) illustrates a binding matrix that includes a relatively low concentration of platelet-shaped connecting elements that are situated in a random orientation. The relatively low concentration of the connection element is illustrated by the presence of filler material around the connection elements; thus, there is at least some dilution of the connecting elements. Due to the concentration and orientation of the connecting elements in FIG. 2 (f), the composite material can be referred to as a percolating mesh. The composite material of FIG. 2 (f) reaches the percolation threshold because a large proportion of the connecting elements are touching each other such that a continuous network of contacts is formed from one end of the material to the other end.
[074] The percolation threshold is the critical concentration above which connecting elements show long-range connectivity with an ordered (FIG. 2 (e)) or random (Fig. 2 (f)) orientation of connecting elements.
[075] In addition to orientation and concentration, the connection elements in the connection matrix can be arranged such that they exhibit a certain pattern of connectivity with the filler. Such connectivity patterns are described, for example, in Newnham et al., “Connectivity and piezoelectric-pyroelectric composites”, Mat. Res. Bull. Vol. 13, pages 525536, 1978).
[076] FIG. 3 illustrates several different connectivity patterns for an exemplary composite material including 0-0, 1-0, 20, 3-0, 1-1, 2-1, 3-1, 2-2, 3-2, connectivity patterns, 3-2, 3-3 and 3-3. In FIG. 3, the exemplary composite material has two components, a first component (shaded) that can represent the bonding matrix, and a second component (un-shaded) that can represent the filler material. The different types of connectivity patterns can be explored to obtain desired material properties associated with the composite material.
[077] FIGS. 4 (a) and 4 (b) illustrate examples of a composite material comprising a bonding matrix (white portion) and equiaxial filler particles or anisotropic fibers, respectively. In the case of FIG. 4 (a), the equiaxial filling particles are arranged in a random orientation, whereas the bonding matrix is aligned along all three axes. Thus, it can be said that the connectivity pattern of the composite material in FIG. 4 (a) is a 3-0 connectivity standard. In the case of FIG. 4 (b), the anisotropic filler fibers are arranged in 1-D orientation with respect to the z direction. Thus, it can be said that the connectivity pattern of the composite material in FIG. 4 (b) is a 3-1 connectivity standard. Again, depending on the desired application and material properties, the filler material can be any one of a plurality of inert and / or active materials. Hierarchical structure
[078] Different types of bonding matrices can be created by varying the porosity of the matrix and incorporating core fibers of different sizes (as noted in Tables 3 and 4 below). If the composition of FB1 is an example of a binding matrix (Table 3), this binding matrix can be used to form repetition levels 1, 2, 3, 4, or higher of hierarchical structures. The level of the hierarchical structure can refer to the number of length scales where an important structural feature is introduced (FIG. 13). Different types of particulate and fiber components can be used with, for example, hierarchical structures of level 1, 2, 3, or higher to manufacture different types of structures with different connectivity as shown in FIG. 3. Table 3: Variation of compressive strength in different bonding matrices formed using different dimensions of core fiber
Table 4: Effect of the porosity of connecting elements manufactured with fiber cores of d50 = 9 μm on the compressive strength

[079] The hierarchy describes as pattern structures at various length scales. The examples described above are, however, an example of how the connecting elements can be used hierarchically in a way that can promote dense packaging, which takes into account the manufacture of a strong material, among other useful, potential functional purposes.
[080] An illustration of the hierarchical structure of multi-level repetition is shown in Figure 13 in which an ordered hierarchical structure can repeat at different length scales, such as 1 or more length scales.
[081] For example, a level 1 repetition hierarchical system can be described as a composite formed by combining two bands of different size or particle size, usually differing by an order of magnitude. Larger size particles can arrange in different types of packaging such as Compact Hexagonal Packaging, or Cubic Compact Packaging, or Random Packaging, but not limited to these, to form a network that contains interstitial voids, and the smaller size particles can accommodate in the voids of the larger particles. Ideally, these hierarchical systems can be prepared using particles of the same size at each level, for example spherical particles with 1 mm in diameter are filling interstitial empty spaces of spherical particles packed with 10 mm in diameter. However, in practice, it is difficult to obtain monodisperse particles, consequently, hierarchical systems will be illustrated using continuous modal particle size distributions. For example, connection elements of type FB1B (d50, ~ 9 μm) can adjust in the voids of filling particles of particle size varying between (100 to 500) μm (Figure 13 (a)). In order to further enhance the connectivity of the connection matrix in the structure, a coating of connection elements of the type FB1B can also be applied to the thicker filling particles and consequently these connection elements of the type FB1B can fill the empty spaces of filling particles. thicker coated (Figure 13 (b)). Another alternative method of fabricating a level 1 hierarchical structure would be to use fine filler particles (<1 μm median particle size) in the voids of the FB1B binding matrix.
[082] For example, the level 2 hierarchical system can be described as a composite of the level 1 hierarchical system combined with larger or smaller particles whose particle size differs in an order of magnitude from the coarser or finer particles in the hierarchy of level 1. For example, in the present example, connection elements of type FB1B in the voids of medium filling particles between (100 and 500) μm, and subsequently this hierarchical system of level 1 evenly distributed in the voids of thicker aggregates from 1 to 5 mm (Figure 13 (c)). In order to further enhance the connectivity of the bonding matrix, a thin coating of the bonding matrix of FB1B (Table 3) can be applied to both thicker and medium filler particles (Figure 13 (d)).
[083] For example, a level 3 hierarchical system can be described as a composite of the level 2 hierarchical system combined with larger or smaller particles differing in an order of magnitude than the largest or smallest particle in the level 2 hierarchy. For example, fine filler particles <1 micron in the voids of the FB1B matrix forming a level 1 hierarchy, and subsequently this level 1 hierarchy in the voids of larger filler particles between 100 and 500 μm forming a level 2 hierarchy, and finally this level 2 hierarchy in the voids of filling aggregates from 1 to 5 mm forming a level 3 hierarchy. Along the same line, a higher order, level n hierarchical system can be generated. As the levels of hierarchy increase, the range of length scales including the various levels also increases. Thus, as n increases to infinity, so does the length scale. This immense range of length scale and hierarchy provides an infinite way to implement our new link element in materials.
[084] It is also possible to use linkers with different particles of different size fraction bands to enhance packaging using hierarchical packaging systems that are not repetitive or random as well. As such, the organization of the particles is non-repetitive and hierarchical - some may consider this hierarchical in structure, but having a different structure in the geometric sense at different length scales, or random packaging involving particles are mixed randomly without incorporating non-random structures. such as interstitial packaging of large pores with particles or thin coatings of one particulate component on top of another.
[085] These packaging strategies can lead to high apparent densities, which can be manifested by small water absorption values. For example, the water absorption of FB1B (Table 3) is 7.7 ± 0.6% by weight (5 h boiling water test, ASTM C 67). If two components of different size bands are used, for example, when FB1B volastonite fiber cores are combined with sand (CPC2, Table 12) the packaging is improved, and the water absorption decreases to 5.3 ± 0, 5% by weight. Similarly, when particles of three fractions of size are used, that is, FB1B volastonite fiber cores combined with sand (particle size between 300 and 500 microns) and basalt aggregates (particle size between 6 and 8 mm), water absorption is further reduced to 3.1 ± 0.9% by weight. Alternatively, if 1% by weight of fumigated silica (d50 <1 μm) is added in the CPC2 type composition then the water absorption is further reduced to 2.6% by weight. Use of the binding matrix
[086] The bonding matrix, including the bonding elements described above can be used to adapt and therefore improve the material properties of almost any article that has a microstructure that can be modified by incorporating the bonding matrix, such as cement or concrete. In one example, the bonding matrix can be used as a partial or complete substitute for Portland cement, and used as a hydrate-free bonding phase for components typically used in a wide range of concrete products, thereby improving the various properties associated with these products.
[087] The material properties of the composite material that can be improved as a result of incorporating a bonding matrix, including bonding elements, according to exemplary embodiments of the present invention, include mechanical properties, thermal properties and durability. However, specific mechanical, thermal and durability properties except those listed in Table 19 can be improved equally. Additional material properties such as optical properties, electronic properties, catalytic properties, nuclear properties and magnetic properties can also be improved.
[088] By way of example, a composite material comprising a bonding matrix according to exemplary embodiments of the present invention may exhibit improved damage tolerance under compression. In the following, exemplary wollastonite particles are generally referred to as having a fiber shape for simplicity. However, volastonite particles can have any morphology generally anisotropic, such as having an acicular or fiber-like shape.
[089] With reference to FIG. 9, a material composed of smaller wollastonite cores (Composition P3 in Table 4, Fig. 9) exhibits fracture with little or no sudden plastic deformation due to compressive stress. However, with reference to FIG. 10 (Composition FB4 in Table 3, Fig. 10), the incorporation of the longest wollastonite fiber cores in the bonding matrix causes a series of slit deflections to occur, where each deflection provides relief (that is, “recovery of damage ”) from the build-up of voltage, thereby delaying the start of the last failure. Another way, in which the bonding matrix may fail due to sudden brittleness with more gradual failure, is by using a plurality of core particle sizes and fine filler particles in the encapsulating layer (Fig. 12). For example, fine particles, such as silica particles, can be dispersed in a bonding matrix with porosity. With reference to compound FB4 in Table 3, the core can comprise particles of three different sizes in three volume fractions. A greater or lesser number of sizes (for example, 2, 4, 5, 6, or more) or different volume fractions can be used. The bonding matrix can then act as a hydrate-free cementation phase in the composite by bonding to itself and the fine particles. Such a composite microstructure would take into account the gradual failure, as shown in FIG. 12.
[090] In this example, the crack propagation mechanism is being changed because of the different interfaces formed in the connection matrix. The core particle (s) can act as a slit deflector. In addition, a first interface is formed between the core and the first layer, and a second interface is formed between the first layer and the encapsulating layer. The two different interfaces can have the same or different resistances. For example, the first interface may have higher interfacial strength (for example, mechanical strength) than the second interface, and vice versa. As a result, after a crack is initiated and begins to propagate, the crack can be deflected from a stronger phase and on the contrary, propagate along the weaker interface, causing it to detach.
[091] It has been shown that a composite material including the bonding matrix can exhibit improved mechanical properties as shown in the present disclosure. Also, as shown in Table 10, the article may have a higher thermal conductivity and a lower coefficient of thermal expansion than conventional Portland cement. In addition, it is believed that various composite materials according to the present invention can also exhibit a wide range of properties, such as those shown in Table 5. It should be understood that exemplary modalities of composite materials can also have properties corresponding to subsets of the ranges listed in Table 5. For example, modalities may include composite materials that have a thermal expansion coefficient between 3 x 10-6 / ° C and 15 x 10-6 / ° C. Exemplary modalities of composite material can exhibit a thermal conductivity greater than about 0.13 W / mk, and less than about 196 W / mk Exemplary modalities of composite material can exhibit a thermal capacity between 6 and 900 J / mol. K. Exemplary modalities of composite materials can exhibit a Vicker hardness between about 1 GPa and 30 GPa. Other exemplary modalities include composite materials that can exhibit a compressive strength ranging from 14 to about 3,000 MPa and a flexural strength of less than about 380 MPa. Exemplary modalities of composite materials can also exhibit strain strain of less than 4.14 x 10-7 MPa (60 x 10-6 / psi). Exemplary modalities of composite materials can exhibit permeability in Cl- of less than 700 C. Exemplary modalities of composite materials can be self-reinforcing and have an impact resistance with a sphere greater than 6 J. Exemplary modalities of composite materials can also be reinforced with steel fibers and have an impact resistance with a sphere greater than 10 J. In addition, exemplary modalities of composite materials may exhibit combinations of the above ranges of properties and / or those ranges of properties listed in Table 5. Table 5: Upper limit and bottom of different properties of composite material according to modalities


1http: //www.matweb.com/search/DataSheet.aspx MatGUID = d8d230a8d966 4bc390199dab7bc56ele & ckck = 1 2http: //www.insaco.com/matpages/mat display.asp M = SIC-RB 3http: // en. wikipedia.org/wiki/Fracture_toughness 4http: //www.hexoloy.com/ 5http: //www.physorg.com/news8947.html 6http: //chemicalproperties.org/property/melting-point/ 7http: // www. ferroceramic.com/Cordierite table.htm 8Kurt Kleiner (11/21/2008). “Material slicker than Teflon discovered by accident”. http://www.newscientist.com/article/dn16102-material-slicker- than-teflon-discovered-by-accident.html. Repaired on 12/25/2008. 9http: //en.wikipedia.org/wiki/Albedo#cite note-heat island-0 10Evans, DA; McGlynn, AG; Towlson, BM; Gunn, M; Jones, D; Jenkins, TE; Winter, R; Poolton, NRJ (2008). "Determination of the optical band-gap energy of cubic and hexagonal boron nitride using luminescence excitation spectroscopy". Journal of Physics: Condensed Matter 20: 075233. doi: 10.1088 / 0953-8984 / 20/7/075233. applications
[092] The connection matrix and / or connection element described herein can be used in a variety of applications. Because of the superior properties of this binding element / matrix as described here, the element / matrix can be used in applications in electronic, optical, magnetic, biomedical, biotechnological, pharmaceutical, agricultural, electrochemical, energy storage, energy generation applications , aerospace, automotive, body and vehicle, tissue, and abrasive and cutting, and any combination of the preceding applications. It can also be used as photochemical, chemical, photoelectric, thermionic and / or electroluminescent separations.
[093] Some of the illustrative examples are provided below:
[094] The bonding element or matrix can be used as a Portland cement similar to the cementitious phase, lime / cement, or related cementitious materials. These solids can be applied in any Portland cement, lime / cement or related cementitious applications.
[095] The linker / matrix can be combined with additives, including CaCO3, or gypsum, and sand, to form monolithic solids. Monolithic solids are solids that are formed as a single piece, without joints or joints. For the purposes of this specification, the term “monolithic” is not being used or intended to be used to describe uniformity at a microscopic level. Examples of monolithic solids can mimic and / or resemble performance as well as the appearance of terracotta, or natural stones, such as granite and limestone. The appearance can be created by forming different colors and textures with additives. In one embodiment, these monolithic solids can be used in any applications where conventional terracotta, or natural stones are used.
[096] The bonding element or matrix can also be combined with sand, or other minerals to prepare mortar or grout, and the resulting material can be used in any applications where conventional grout and grout are used.
[097] The connecting element / matrix can also be combined with metallic, organic, or ceramic fibers to manufacture a fibrous cement. The resulting material can be used in any applications where conventional fibrous cements are used.
[098] The connecting element or connecting matrix can be used in hydrate-free concrete applications. In one embodiment, it can be combined with sand and aggregate and / or aggregates to form a material that mimics and / or resembles regular or structural concrete. The resulting material can be used in any applications where conventional structural or regular concrete is used, for example, dams, bridges, swimming pools, houses, streets, patios, basements, handrails, flat cement tiles, mosaic tiles, pavement blocks, lampposts, drain covers, or combinations thereof.
[099] By carefully adjusting particles, dispersants, and / or residues, such as cork, glassy aggregates, resulting materials that mimic and / or resemble high-strength concrete (HSC), 3D fiber-type structures (for example , concrete blankets), fast-lasting concrete (RSC), cork-based composites, glassy concrete, and high-performance concrete (HPC) can be produced. The resulting material can be used in any applications where conventional HSC, concrete blankets, RSC, cork-based composites, glassy concrete, HPC are used.
[0100] Steam and / or vacuum during the process can also be used to produce material that mimics / resembles Vacuum Concrete (VC) and that can be used in any applications where conventional VC is used. In an alternative modality, by controlling the porosity, a resulting material that mimics / resembles permeable concrete can be produced. The material can be used in any applications, where conventional permeable concrete is used.
[0101] In one embodiment, the bonding element / matrix is combined with fibers, sand, aggregates, and / or other additives, such as defoamers and / or ultrafine particles, such as fumigated silica and CaCO3, to prepare fiber-reinforced concrete (FRC) that performs as fiber-reinforced composites and / or ultra-high performance concrete (UHPC). These solids can be used in any applications, where conventional FRC and / or UHPC are used. In an alternative modality, by controlling the flow (for example, adapting the water content during processing), other types of installation of concrete products can be produced. The products included shotcrete, self-compacting concrete, concrete compacted by cylinder, or combinations thereof.
[0102] In another embodiment, the bonding element / matrix is combined with a metal such as aluminum and Ca (OH) 2 and autoclaved, or by controlling the porosity using different auxiliaries such as vacuum, or entrainment of air to produce a material that mimics / resembles autoclaved aerated concrete (AAC). This material can be used in any applications where conventional AAC is used.
[0103] In an alternative embodiment, the connecting element / matrix is combined with low density sand and / or aggregates (for example, expanded vermiculite and perlite, pumice, expanded slag, expanded shale, or combinations thereof), and by controlling the porosity, these composites can be used as lightweight concrete or cellular concrete, lightweight aerated concrete, variable density concrete, lightweight concrete or lightweight concrete or any other material related to these types of concretes. In another embodiment, the bonding element / matrix is combined with high density aggregates (for example, density> 3.2 g / cm3), and the resulting product can be heavy concretes.
[0104] The connecting element / matrix presently described can be used in combination (and thus reinforced) with steel to manufacture reinforced concrete material, which can be used in any applications where reinforced concrete structures are used. The material can be pre-tensioned to imitate / resemble prestressed concrete. In one embodiment, the connecting element / matrix can be poured into very large blocks to produce a material that mimics / resembles mass concrete. Applications for these types of bulk concrete material can include dams, breakwaters, or a combination of these. The concrete derived from the connection element / matrix presently described can also be manufactured with different textures for decorative purposes.
[0105] In some embodiments, a composite material comprising the currently described bonding element / matrix may have superior properties. For example, it can have excellent corrosion resistance, such as providing protection to steel reinforcement in an environment with a high chloride content, and excellent durability in aggressive sulphate environments. A composite material can be used in highly specialized applications, such as sound protection and / or protection against nuclear radiation. In one embodiment, the material may have desirable flame resistance, and may be suitable for refractory applications. The material can also withstand extreme weather conditions, such as, for example, freezing conditions, high desert temperatures, or extreme weather fluctuations, and / or freeze-thaw resistance. The material may also be suitable for use in specialized marine, cryogenic, and / or burst resistance applications. In some embodiments, the material can be used in earthquake-resistant structures and / or geosynthetic-type structures. NON-LIMITING WORK EXAMPLES Example 1
[0106] FIGS. 5a and 5b show SEM images of secondary electron (SE) and backscattered electron (BSE) of randomly oriented CaSiO3 core fibers coated predominantly by amorphous silica, and these coated fibers are encapsulated with CaCO3 particles. The chemical mapping by EDS in FESEM of the microstructure showed that volastonite core fibers are coated by regions rich in SiO2 and encapsulated by CaCO3 particles (FIG. 6). Different binding matrix elements are held together by CaCO3 particles. XRD of this composition revealed that CaSiO3 and CaCO3 (calcite) are crystalline phases whereas regions rich in silica are amorphous.
[0107] Table 6 compares mechanical properties of conventional monolithic materials with different compositions (Tables 3 and 4) formed using a bonding matrix based on volastonite core fiber. These connection matrices showed a range of compressive strengths between 40 and 300 MPa. In addition, the compressive strength can be adapted both by the size of the fiber core unit and by the porosity. The highest strength observed in this bonding matrix has a strength comparable to a stone of size such as granite. Samples of FB1A and FB1B were prepared by compression and casting methods, respectively, before conducting the disproportionate reaction. These two different ceramic forming techniques leave materials with slightly different compressive strengths because of different modes of the raw material package (Table 3). In addition, smaller samples based on FB1A matrix (diameter = 12.8 mm) with an average resistance of 298 ± 5 MPa were observed. These results indicate that it is possible to further enhance the resistance in these solids by reducing the defect populations even further by more advanced processing. There are many conventional methods of powder processing that can be used to reduce defect populations and in turn leave larger samples at results that have these improved mechanical properties. This optimization process is possible with someone of ordinary skill given the use of this new linker technology. Table 6: Comparison of compressive strength of different materials
1Anne Duperret, Said Taibi, Rory N. Mortimore, Martin Daigneault, Effect of groundwater and sea weathering cycles on the strength of chalk rock from unstable coastal cliffs of NW France ”, Engineering Geology 78 (2005) 321 343. 2S. Mindess, JF Young, and D. Darwin, Concrete, Second Edition, Prentice Hall (2003). 3http: //www.supremesurface.com/granite/granite.html, 4http: //content.wavin.com/WAXUK.NSF/pages/Terracotta-Performance-Data- EN / $ FILE / performance_data.pdf
[0108] FIG. 7 shows a Vicker Hardness Indentation in a composite material with the microstructure described in example D (composition P3, Table 4). This composite material had a hardness of ~ 1.6 GPa. Cracks emanating from the corner of the indentation were subsequently studied to understand crack propagation (FIG. 8). Regions B and D show that the slit deviated around different core fibers of wollastonite by detachment at the interface between regions rich in silica and rich in CaCO3 (FIG. 8 (a)). These core fibers act as slit deflectors, and slits subsequently deflected around them and propagated through CaCO3-rich phases present at interface boundaries (FIG. 8b). Consequently, the interface between the silica-rich coated region and CaCO3 is weak when compared to the robust interface between the core volastonite grain and the silica phase coating (FIG. 8 (c)). This single interface structure can be used to design structures in which cracks are deflected by detachment which increases the damage tolerance of these structures against failure due to sudden fragility. The composition P3 showed failure due to fragility and had a compressive strength of 110 MPa (FIG. 9) and a tensile strength of 12 MPa.
[0109] It is also possible to adapt the hardness of these composite materials by making composite materials with different additives such as carbides, silicates, glass, and vitreous ceramics or even different types of metals and polymers. For simplicity, hardness calculations are made assuming 30 %% in volume of P3 bonding matrix combined with different additives, and subsequently, using a mixing calculation rule, different range of hardness values can be calculated. For example, by adding BeO, a hardness of 1 to 1.3 GPa can be obtained, and by adding B4C, a hardness of 21 to 27 MPa can also be obtained as shown in Table 7. In other exemplary embodiments, the material it can have a Vicker Hardness between about 1 GPa and about 30 GPa. Table 7: Summary of the calculated hardness values of different composites made with P3 connection elements.


[0110] Similarly, connecting elements can also be used to affect thermal conductivity. Also, the connecting elements can be used to affect thermal expansion. Exemplary modalities of these variations are provided in Table 8. Table 8: Summary of thermal conductivity and thermal expansion calculated from different composites manufactured with P3 connection elements [1-6]


[0111] Tables 3 to 4 show how the compressive strength varies with the size of the core fiber. As the average size of the core fibers was decreased from 70 to 9 microns, the compressive strength increased from 60 to as high as 300 MPa but stress versus displacement curves as in Fig 9 show that these materials undergo catastrophic fracture with little or no impact. no plastic deformation (unattractive failure).
[0112] Composition FB4 is developed using very large core fibers (~ 2800-150 μm) of different size fractions to communicate damage tolerance. Initially during the measurement of stress versus displacement (FIG. 10), the stress varied linearly with displacement. After reaching a final compressive strength (UCS) of 72 MPa, the stress dropped quickly due to the failure, afterwards the sample recovered its original strength (a sign of damage tolerance or in other words, attractive failure or ductility or ductile failure); subsequently this cycle continued 3 times before the failure. Thus, the interfacial structure played a major role in the damage tolerance of this binding matrix (FIG. 10). These types of structures will be referred to as “Self-reinforced Cementitious Composites (SRCC)”. In this case the novelty is that fiber-based connecting elements are acting both as cement units (active fibers or filler), as well as, they are also acting as slit deflectors for damage tolerance.
[0113] In summary, core fiber sizes play a major role in controlling the mechanics of the binding matrix. If the average particle size of the core fibers is small (about <70 μm) then these bonding matrices show large compressive strengths (as high as 300 MPa) with fragile rather than attractive fracture or failure. If large core fibers (150 to 2800 μm) are used (composition FB4, Table 3) then the crack deflection and detachment of these large active fiber interfaces play an important role in inducing damage tolerance (or ductility or attractive failure) .
[0114] By controlling porosity in a randomly oriented bonding matrix composed of core fibers of volastonite with an average particle size of 9 μm, a wide variety of structures can be created. Table 4 shows the effect of porosity on the compressive strength of the bonding matrix. The decrease in porosity from 45% to 17% in the bonding matrix caused an increase in the compressive strength of the bonding matrix from 10 MPa to 163 MPa.
[0115] The example above shows how the properties of these materials can be changed. There are many microstructures where this connecting element can be used. Example 2
[0116] FIG. 11 shows the interaction of SiO2, Fly Ash with high Ca content (HCFA) and CaCO3 with the P3 binding matrix (composition P3, Table 4). Observation of the P3 binding matrix and SiO2 interface (FIGS. 11 (a) and (b)) reveals that CaCO3 particles and a silica-rich coating around the volastonite core fibers formed an bonded interface with silica particles externally added. At the interface of the P3-HCFA binding matrix, there was no sign of detachment between the HFCA and the binding matrix (FIG. 11 (b)). Similarly at the P3-CaCO3 binding matrix interface, externally added CaCO3 particles formed diffuse interfaces with binding elements.
[0117] FIG. 12 (a) shows a typical example of composite 0-3, where 70% by volume of particulate components of sand (silica) are dispersed in the P3 bonding matrix with porosities in the structure (Table 4). This composite material showed a gradual failure during compression, and had a compressive strength of -55 MPa (FIG. 12 (b)). 30 %% by volume of P3 bonding matrix are acting as the hydrate-free cementation phase in the composite material bonding to itself as well as to the sand particles.
[0118] FIGS. 14 (a) and (b) show optical micrographs of a composite material formed using a 1: 2: 2 volumetric ratio of FBI Fiber Cores, (300 to 500) μm of sand, and (2 to 4) mm of sand aggregates, respectively. At higher magnifications, it can be seen that the bonding matrix is in the empty spaces of sand particles, and a thick layer of bonding matrix surrounded sand particles to act as a cementation phase as well. Table 9 shows the ASTM property test certified by CTL, Illinois and the mechanical properties of the present microstructures in one embodiment. These values should not be seen as limiting but only as examples. For example, additional modalities may include composite materials with an abrasion resistance having an average wear of less than 1.00 mm using ASTM C 944 instead of having to be exactly 0.38 mm. This composite material has mechanical properties like high performance concrete, in which case 20 %% by volume of bonding matrix was used to bond the entire structure. Table 9: ASTM certification of typical hydrate-free concrete (HFC4) by CTL (Construction Technology Laboratory, Skokie, Illinois)

5http: //www.fhwa.dot.gov/BRIDGE/HPCdef.htm. Example 3:
[0119] FIG. 15 shows the variation of the thermal tension of FB1B from -40 to 100 ° C during the thermal cycling for 2 consecutive cycles. No signs of thermal hysteresis, or phase changes were observed during thermal cycling. Table 10 summarizes the thermal properties of compositions P2 and P3. FIG. 16 shows the variation of specific heat from room temperature up to 500 ° C of P3 (Table 4). The specific heat gradually increased from 0.711 (J / g2C) to 1.274 (J / g- ° C). No change in phase or change in thermal properties of the P3 composition was observed. Clearly, similar types of bonding elements in their pure form, or incorporated into the composite composition can be used in high temperature applications such as flame resistance etc. Table 10: Summary of thermal properties of compositions P2 and P3 (Table 3)

[0120] Using Table 10, the thermal conductivity and thermal expansion of different composite materials using connection elements and using a simple rule for approximating mixtures can be calculated. For example, a 30 %% composite material by volume of P3 bonding matrix with cork will have a calculated thermal conductivity of 0.55 W / m.K. Similarly, a composite material of 30% by volume of P3 binding matrix with AlN can have thermal conductivity between 146 and 196 W / m.k. In addition, these values can be regulated by varying the content and porosity of the connecting elements. For example, it is also possible to use 10 %% by volume of porous P2 matrices to bond perlite and have thermal conductivity as low as 0.13 W / m.K. In summary, there are numerous combinations and permutations that can be used to adapt thermal properties.
[0121] Preliminary results also showed that FB1A samples were able to withstand 10 cycles of thermal shock of 200 ° C and then extinguish them in water. Example 4:
[0122] Properties such as combined cements, high-strength mortars, and stones such as Granite, Sandstone, and Terracotta.
[0123] Bonding matrices based on volastonite (Tables 3 and 4) have the appearance of marble or limestone. They can be used as an architectural building material in a pristine form for decorative purposes. It is also possible to adapt the appearance by adding different coloring additives (Table 11). FIG. 17 shows typical examples of sandstone, granite, and terracotta mimics prepared by adding dyes to the bonding matrix. The CPC composition series (Table 12) was used to prepare different sandstone mimics. Since bonding elements are combined with sand so that these compositional materials can be used as substitutes for mortar, grout, or high-strength structural bricks as well. Similarly, by adding different colors to the connection matrix (Tables 3 and 4) different types of colors and textures can be generated. In such a way, the composite material can be manufactured to exhibit color and texture resembling the natural stones described here. Alternatively, the composite material can be manufactured to exhibit color and texture resembling the architectural concrete described here. Table 13 summarizes the physical properties of different stones. Except for Quarzite and Granite, compressive strengths of all listed solids are less than 69 MPa. The average compressive strength of all composite materials other than the CPC series is greater than 69 MPa (Table 12). In addition, the average compressive strengths of FB1A and FB1B compositions (bonding matrix without any additives, Table 3 and previous discussion) are between 147 and 300 MPa. Clearly, physical properties of geomimetic ceramic materials are better than natural stone. Using the concept explained earlier, it is also possible to imitate other natural rocks such as traventine, serpentine, etc. Table 11: Different types of dyes
Table 12: Summary of the compositions of different combinations
: All compositions are in %% by volume * Certified by CTL (Skokie, IL) Table 13: Physical properties of different stones

[0124] In addition, it is also possible to manufacture structures with low water absorption as well. For example, CPC2 (Table 12) has a water absorption of 5% by weight. It is already comparable to sandstone (Table 14). By adding 1% by weight of fumigated silica (d50 <1 μm) in CPC2 type combinations, the water absorption can be further reduced to 2.6% by weight. Table 14: Compressive strengths of high-strength hydrate-free concretes (CTL certified)
: All compositions are in %% by volume * Certified by CTL (Skokie, IL)
[0125] Basalt density = 2.9 g / cc, wollastonite density = 2.9 g / cc, dolomite density = 2.7 g / cc, sand density = 2.6 g / cc, CaCO3 density = 2.7 g / cc, steel density = 7.8 g / cc, gravel density = 2.6 g / cc Comparison of structural concrete with HFC.
[0126] Structural concrete has a compressive strength of 35 MPa. By making a composite material of wollastonite core fibers with sand and different types of aggregates, it is possible to obtain a wide variety of strengths that are comparable to structural concrete. Table 15 shows some simple hydrate-free concrete (HFC) compositions, which showed resistance similar to that of structural concrete and, therefore, adequate in all structural concrete applications. Table 15: Compressive strength of different hydrate-free concrete compositions
: All compositions are in %% by volume * Certified by CTL (Skokie, IL)
[0127] The initial composition is described here as the “composite” instead of describing the final composition. The exact final product in terms of chemical composition and phase is unknown. On the other hand, the initial composition can be precisely specified. This is true for all the examples described, not just this one. Comparison of High Strength and Performance HFCs with HSC (High Strength Concrete) and High Performance Concrete (HPC)
[0128] As discussed in a more initial example, the HFC4 composite material performs as a high performance concrete in mechanical strength (Table 9). In addition, it also has permeability in Cl permeability as Grade 1 HPC. Interestingly, HFC4 has high abrasion resistance, fouling resistance and reduction as Grade 3 high performance concrete. It is interesting to note that even without the addition of mixtures air entrainment, HFC4 survived 300 freeze-thaw cycles as specified by ASTM C666, however, its DF (Durability Factor) decreased to 10. Modifications to the sand and aggregate components of concrete formulations can increase this Durability Factor for 93 after 163 cycles per ASTM C666.
[0129] Using advanced processing methods, the best packaging can be achieved in HFC composite materials (Table 14). For example, water absorption decreased from 8.3% by weight in HFC4 to 3.1 and 4.7% by weight in HSHFC1 and HSHFC2. As expected, the compressive strength has also increased in these composite materials. HFC4 showed a compressive strength of 47 MPa while the compressive strengths of HSHFC1 and HSHFC2 increased to 80 MPa and 65 MPa, respectively.
[0130] Initial Strength Cement or Concrete
[0131] FIG. 18 shows the variation of the reaction time in the mechanical resistance. After a reaction time of 5 h, a compressive strength of 60 MPa is achieved. These systems can be used to prepare the initial strength cementation phase, or as concretes in composite systems. Portland cement concrete does not do this in such a short time.
[0132] Comparison of HFC Compositions Engineered with UHPC (Ultra-High Performance Concrete)
[0133] FIG. 19 shows the typical ductile failure of the FB1B bonding matrix reinforced with 10% by weight of DRAMIX steel fibers (ZP305, Bekaert Corporation, Marietta, GA). DRAMIX is a proprietary low-C cold drawn steel fiber having a length of -30 mm and a diameter of -0.5 mm with curved ends glued together. However, it is expected that similar results can be obtained with several other steel fibers.
[0134] The CPC2 type composition (Table 12) was also infiltrated with 10% by weight (4 %% by volume) of steel fibers (FRCPC2, Table 16). These compositions showed flexural strength approximately 1.4 times higher than the CPC composition and simultaneously also ductile failure (Fig. 19 b). Similarly, when CPC2 was infiltrated with 2.5% by weight of PVA fibers (RFS400, NYCON PVA, 18 mm fibers, Fairless Hills, PA), they would then fail at a lower resistance, but showed enhanced resistance retention. Table 16: Summary of different compositions manufactured by modifying CPC2
All compositions are in %% by volume
[0135] In order to adapt and enhance the interaction of connecting elements with steel, these fibers were allowed to oxidize in air (formation of rust). Subsequently, 10% by weight (4% by volume.) Of rusted fibers were also placed in the CPC2 matrix (RFRCPC2, Table 16). Due to the enhanced detachment at the interface, these new compositions showed enhanced ductility (region II in Fig. 19c). FIG. 20 shows the steel-matrix connection interface. Clearly, during the curing reaction the original interface interacted with the steel surface. These composite materials are referred to as “hydrothermally controlled interfacially engineered ductile compounds”.
[0136] It is believed that the steel fiber interface can have a single composition and structure.
[0137] Table 17 shows the property comparison of Ductal® (An ultra-high performance concrete owned by Lafarge (US / Canada Region, Calgary, Alberta, Canada, T2W 4Y1) with FB1B (a bonding matrix with based on volastonite core fiber, Table 2B)). FB1B has higher compressive and flexural strength when compared to Ductal®-FO (without heat treatment), but slightly lower compressive and flexural strength when compared to Ductal®-FM or Ductal®-AF (Ductal®-FM with heat treatment) . The thermal expansion of FB1B is higher than all the different varieties of Ductal®. FB1B has fragility failure. Using steel fibers and additional particle and fiber engineering, it is possible to manufacture composite materials with ultra-high performance. These materials can potentially be used in all applications of ultra-high performance concrete materials, which will be discussed in the next section. Table 17: Comparison of bonding matrix properties based on volastonite core fiber with Ductal® (A type of ultra-high performance concrete)

New Ductile and Impact Resistant Structures
[0138] Table 18 summarizes different composite materials manufactured using longer volastonite fiber cores (d50 = 800 μm). FIG. 21 shows a typical microstructure of SRC3 composite materials (Table 18). As the concentration of longer fibers increases in these self-reinforcing structures, the flexural strength decreases, however, as summarized in Table 20, the impact resistance improves even more. For example, the pristine FB1B binding matrix fails at 0.75 ft.lb impact, whereas when they are self-reinforced with longer fiber cores, they fail at 4.5 ft.lb impact. Traditional monolithic materials like Granite, Travertine, Marble fail at 1.2 ft. lb, while Pittsburgh Corning Thickset 90-approved Metro-Dade (Pittsburgh Corning Corporation, Pittsburgh, PA) fails to impact 2.2 ft.lb. It is clear that SRCC has one of the highest impact strengths among different types of construction materials. Table 18: Summary of compositions of self-reinforced composites
: All compositions are in %% by volume Supercombination
[0139] In earlier examples, concepts of “Self-reinforced Cementitious Composites (SRCC)” and “Hydrothermally Controlled Interfacially Engineered Ductile Composites” were explained. It is possible to integrate these two methods and manufacture a new class of materials called Supercombination (Table 19). FIG. 22a shows the ductile behavior of the composite material FSRBC1. Four main regions were observed during the deformation: (I) Elastic, (II) Plastic, (III) Retention of force, and (IV) Gradual failure. FIG. 22b shows the flexion of this composite material during the 3 point flexion. These solids have high impact resistance (Table 20). For example, FSRBC1 has an impact resistance of 13 ft.lb, which is about 6 times higher than that for Pittsburgh-Corning Thickset 90. Table 19 Different compositions used to manufacture supercombination

: All compositions are in %% by volume Table 20 Impact resistance of different compositions using impact with sphere (Certified by Trinity / ERD, Columbia, SC)

[0140] These types of solids can be used for applications that require burst and impact resistance properties, concrete-like properties of ultra-high performance and high performance, damage-resistant applications such as adverse freezing, high-freeze applications. In addition, it is possible to replace the combination with different types of additives according to specialized applications such as sulfate resistance, chloride resistance etc., but not limited to these. Table 19 shows an example where dolomite fillers can also be used instead of CaCO3 or sand. Example 5 New Bonding Element Chemistry
[0141] Similarly, it is also possible to design a wide range of structures using chemicals other than volastonite above, but they have the common ability to use the disproportionate reaction to form the new linker described in this invention. For example, Figs. 23 and 24 show microstructures of binding matrices derived from olivine (Mg2SiO4) and diopside (MgCaSi2O6) precursors. These bonding matrices have a compressive strength of 162 ± 15 MPa and ~ 93 MPa, respectively. For example, Olivine is composed of an unreacted Mg2SiO4 core surrounded by unreacted silica layers (suppression zone) and MgCO3 crystals acting as a cementation phase to bond the entire structure (Fig. 23c). These unreacted nuclei may have different morphologies, for example, Fig. 23d shows how MgCO3 crystals precipitated within cupuliform olifin grains.
[0142] Fig. 24 shows microstructures of diopside grains as nuclei. These grains are surrounded by amorphous silica, and dolomite (CaCO3 ^ MgCO3) and / or magnesite (MgCO3) and / or CaCO3 particles. As with volastonite, these materials can be used to manufacture new microstructures using the various methods described earlier. In addition, as mentioned earlier, there are a very large number of ceramics that can undergo this disproportionate reaction, which are both minerals and waste products.
[0143] It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention includes the modifications and variations of this invention as long as they fall within the scope of the appended claims and their equivalents.

权利要求:
Claims (13)
[0001]
1. Composite material comprising: a bonding matrix and a filler material incorporated in the bonding matrix, the bonding matrix, characterized by the fact that it comprises: a core, in which the core has a first chemical composition comprising CaSiO3 or MgSiO3 ; a first layer containing silica covering at least partially a peripheral portion of the core, wherein said first layer has a second chemical composition which is a chemical composition different from the first chemical composition, the second chemical composition including the Si cations corresponding to one of the chemical elements of the first chemical composition; and a second layer containing calcium carbonate and / or magnesium carbonate covering at least partially a peripheral portion of the first layer, wherein the second layer has a third chemical composition which is a different chemical composition from the first and second chemical compositions, being that the third chemical composition includes Ca and / or Mg cations which correspond to chemical elements of the first chemical composition, in which the bonding matrix is prepared from a porous solid body, the porous solid body comprises a plurality of precursor particles, the particles precursors have an average particle size of less than 70 μm and the precursor particles are transformed into the connecting elements, wherein the filler material comprises a first plurality of first size particles and a second plurality of second size particles, particles of second size being substantially larger in size than the first particles size, the first size particles and the second size particles are arranged so that the composite material forms a hierarchical structure.
[0002]
2. Composite material according to claim 1, characterized by the fact that the first chemical composition includes at least two different chemical elements, in which the cations associated with the second chemical composition correspond to a first of at least two different chemical elements of the first chemical composition, and in which the cations associated with the third chemical composition correspond to a second of at least two different chemical elements of the first chemical composition or correspond to the first of at least two different chemical elements of the first chemical composition.
[0003]
3. Composite material, according to claim 1, characterized by the fact that the core is equiaxial, elliptical, fiber-shaped, symmetrical or flake-shaped.
[0004]
4. Composite material according to claim 1, characterized by the fact that the first layer is an amorphous layer or a crystalline layer.
[0005]
5. Method for making a composite material, as defined in claim 1, characterized by the fact that it comprises: providing a precursor material that comprises the plurality of precursor particles, in which the precursor material has porosity; mixing the precursor material with a filler; introducing a liquid solvent into the pores of the precursor material; and introducing a gaseous reagent into the pores of the precursor material, whereby precursor particles are transformed into connecting elements having the core, the first layer and the second layer, in which the core comprises the chemical elements M, Me and O (oxygen ) and / or OH group, where M is an alkaline earth metal selected from calcium or magnesium, and Me comprises silicon, in which the first layer containing silica covering at least partially a peripheral portion of the core, in which said first layer has a chemical composition different from the chemical composition of the nucleus, and includes Si cations corresponding to one of the chemical elements of the chemical composition of the nucleus, and in which the second layer containing calcium carbonate and / or magnesium carbonate covering at least partially a portion peripheral layer of the first layer, in which the second layer has a different chemical composition from the chemical composition of the core and the first layer, and includes Ca and / or Mg cations that correspond to chemical elements in the nucleus.
[0006]
6. Method according to claim 5, characterized in that at least a portion of the precursor particles does not react with the reagent and remains to form the core of the linkers.
[0007]
Method according to claim 5, characterized in that the step of introducing a liquid solvent into the pores of the precursor material comprises saturating the precursor material, so that the liquid fills the pores of the precursor material.
[0008]
8. Method according to claim 5, characterized in that the step of introducing a liquid solvent into the pores of the precursor material comprises partially filling the pores of the precursor material with the liquid.
[0009]
9. Method according to claim 8, characterized by the fact that the step of introducing a liquid solvent into the pores of the precursor material further comprises: evaporating the liquid; and condensing the liquid in such a way that the liquid is distributed through the pores of the precursor material.
[0010]
10. Method according to claim 5, characterized by the fact that the filler material includes the inert material.
[0011]
11. Method according to claim 10, characterized in that the inert material comprises a plurality of equiaxial particles, a plurality of anisotropic particles, or a combination thereof.
[0012]
12. Method according to claim 5, characterized in that the step of providing a precursor material comprising a plurality of precursor particles comprises aligning the precursor particles in a desired orientation.
[0013]
13. Method according to claim 12, characterized in that the desired orientation is a 1-D orientation, a 2-D orientation or a 3-D orientation.

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法律状态:
2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2018-04-24| B27A| Filing of a green patent (patente verde)|

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2018-05-15| B27C| Request for a green patent denied|

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2019-07-16| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

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2020-03-03| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|

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2020-08-11| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|

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2020-12-29| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-03-09| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 02/03/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201161449659P| true| 2011-03-05|2011-03-05|

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US61/449,659|2011-03-05|

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