A device of cell / units for making biomineralized concrete products useful for hydrogen generation, transportation, and storage

Abstract

One of the key net-zero challenges is hydrogen transportation with a viable infrastructure delivering it from where it is produced to the point of end users since delivering of hydrogen is still a local, much smaller sized than Liquid natural gas pipeline due to technical and economic barriers, including the embrittlement of the installed steel pipeline on its life cycles, the degradation of the reinforced plastic composites, the high processing cost of ceramic matrix composites, the need for reducing the cost of water splitting reaction. Alternative solutions are needed to resolve the above issues. Inspired by the plant growth in nature, coupled by the piezoelectric effect of microcrystalline silica sand with bio-inspired self-healing chemical additives and mixed in concrete materials, a simplified design of concrete pipeline units is disclosed here that not only stores the hydrogen in a sealing confinement but also manufacture hydrogen, simultaneously releasing oxygen into atmospheres. Experimental examples are disclosed here to demonstrate the utility of the unit's applicability. The outlook of the products is bright for long-distance transportation of hydrogen in the hydrogen superhighway.

Description

[0001] TITLE: A Device of Cell / units For Making Biomineralized Concrete Products Useful for Hydrogen Generation, Transportation, and Storage

[0002] SPECIFICATION

[0003]

[0001] As disclosed in Figure 1, a m ini-cell / unit of device that can harvest renewable energy through energy conversion of self-propelling generators of hydrogen, consisting of: 1) cathode electrode (membrane)-101 ; 2) anode electrode (membrane)-102; 3) permeable electrolysis membrane (PEM)-103; 4) hydrogen in gas phase-104; 5) oxygen in gas phase-105; 6) rectifier - 106; 7) support layer 1 - 107; 8) support layer 2-108; 9) conduct wires-109; 10) water used for water splitting reaction-110; 11) piezo-electric layer 1 -111 ; 12) piezoelectric layer 2-112; 13) Zone 1 (electrolysis)-113; 14) self-propelling energy generator (Zone 2 & 3)-114.

[0004]

[0002] By mimicking the plant growth in nature, this patent application claims the benefit of u. s. provincial patent application of 62 / 704,846 filed on December 2, 2022, in the title of:" multifunctional coatings and chemical additives for making biomineralized concrete products useful for hydrogen transportation and storage", disclosed an unique design of utilizing a self-healing concrete material for generating, storing, and transporting hydrogen along and cross the pipelines as an alternative to steels or other metal materials for building the hydrogen's super highway in the infrastructural construction. The water splitting reaction occurring cross the pipeline cross-sections is disclosed as a key device to resolve the issues of hydrogen storage and transportation in the effort of energy transition for decarbonization.

[0005] DISCLOSURE OF BACKGROUND INFORMATION

[0006]

[0003] FIGURES

[0007]

[0004] Figure 1, a cross-section drawing of hydrogen self-propelling generation, pipeline storage and transportation unit is consisting of: 1) cathode electrode (CE)-101 ; 2) anode electrode (AE) - 102; 3) permeable electrolysis membrane (PEM) -103; 4) hydrogen -104; 5) oxygen -105; 6) rectifier-106; 7) support 1-107;

[0008] 8) support 2-108; 9) electricity wire-109; 10) water used for splitting reaction generating oxygen and hydrogen-110; 11) piezoelectric composite layer 1 - 111 ;

[0009] 12) piezoelectric composite layer 2 - 112; 13) electrolysis layer (zone 1) - 113; 14) self- propelling energy generators (zone 2 & zone 3) -114.

[0005] Figure 2. Proposed hydrogen membranes for hydrogen production and storage in an enclosed space:

[0001] water / heat permeability membranes including a) anodic electrode membrane (AEM): - 201 ; b) cathodic electrode membrane (CEM) -202; c) intermediate solid - state membrane (ISSM) - 203; [2] exterior battery for water splitting reaction and electricity generated flux of moisture and hot air converted from the mechanical stress of sintered microcrystalline quartz- 204.

[0010]

[0006] Figure 3: The figure was adapted from Wikipedia. It shows how two-phase materials interacted with each other in a porous rock material at 10 mD.

[0011]

[0007] Figure 4. Schematic of hydrogen transportation pipeline and storage tanker of 14 functional categories: 1. Hydrogen storage membrane (HSM) -401; 2. Hydrogen storage chamber - 402; 3. Intermediate layer of HSM - 403; 4. Structure frame support -404; 5. Wind farmer for electricity -405; 6. Solar power generator - 406; 7. Surrounding carbon black / clay / soil layers - 407; 8. Funnel for water / rains - 408; 9. Hydraulic pumping system -409; 10. Electrolysis for oxygen -410; 11. Electrolysis for oxygen - 411; 12. Pipeline for clear water transportation - 412; 13. Energy storage water tanker - 413; 14. Central automatic control unit -414.

[0012]

[0008] Figure 5: Designated frame of cell / units: 1) copper wired cross-sectioned with 0.8 (mm) copper wires prolonged to 1.2" on both sides. Wood frame has a Hight of 1 ", A squared mesh of 1" for each cell / unit was prepared. The formed flatten panels have excellent conductivity due to including copper wires in the flatten panels.

[0013]

[0009] Figure 6: A circular loop consisting of 220 (v) batteries, LED light has a one direction for lightening the cell / units. A direct digital sensing (DDS) can create a special wavefunction that controls the piezoelectric output from the conversion from thermal, mechanical, moisture cycling. DDS, LED, and rectifier are in a series of modes during the operation.

[0014]

[0010] Figure 7: A plot of cell / unit voltage vs. its current when a triangular wavefunction was generated by the DDS at different scanning rate from 1 (Hz) to 60,000,000 (Hz) at 7.5 (v).

[0015]

[0011] Figure 8: Plot of log voltage vs. log current that clearly shows the piezoelectric effect of looped circular systems.

[0016] FIELD OF INVENTION

[0017]

[0012] Conceptually, the above cell / units can allow the manufactured pipeline successfully made into desirable size and length as engineered products. Inspired by the plant growth of nature, it was discovered that a composite made of the microcrystalline silica plus AquLuMaxTMcan be used as an energy harvester like a solar panel to convert the cycled moisture, water, and thermal flux originated from surrounding soil into the electricity, potentially power the water splitting reaction by an energy scavenging mechanism. That is, an extruded pipeline product made of the previously described cell / units will not only seal hydrogen (104) from leaking for storage, but also manufacture the evolution hydrogen (104) and oxygen (105) with water (110) splitting reaction, powered by exterior electric grid, and preferred by self-energy harvesting of flexible piezoelectric pipelines (114) that convert daily cycling heat, moisture, and water from surrounding soils.

[0018]

[0013] This multifunctional solid-state concrete, served as both structural support of pipeline (107 and 108) and piezoelectric electrode membrane can potentially harvest daily thermal flux and hydraulic water / moisture into electric energy from surrounding soil to power water splitting reaction composed of a) an anodic electrode membrane (102); (b) a cathodic electrode membrane (101); c) permeable intermediate solid-state membrane {ISSM) (103) between CA and AE membrane.

[0019] [14J In the AEM side, oxygen evolution reaction (OER) can be expressed in equation (1):

[0020]

[0015] 2 H2O (aqueous)

[0021]

[0016] In the CEM side, the hydrogen evolution reaction (HER) occurs:

[0022]

[0017] 4 H+(Aqueous)+ 4 e ’1

[0023]

[0018] Between AE and CE, hydrogen ion will pass through permeable electrolysis membrane (PEM-103) driven by hydraulic dynamic pressure and Gibb's energy by controlling the porous structure and surface texture of chemical compositions in the PEM media.

[0024]

[0019] The water splitting process, involved in the disclosed hydrogen storage, transportation, and generation of alternative electricity from piezoelectric pipelines is consisting of:

[0025]

[0020] water, for splitting into hydrogen and oxygen (110) injected in the anode side.

[0026]

[0021] Membrane (102) that can convert water into oxygen and hydrogen ion as illustrated in equation (1).

[0022] The hydrogen ion created between the interphase of anode layer and permeable layer of PEM (103) will migrate itself from the AE side to CE side driven by thermal dynamics equilibrium of Gibb's equation.

[0027]

[0023] pH value in the PEM (103) is a critical factor that controls the migration of ions in the PEM solution.

[0028]

[0024] When two hydrogen ions migrated to the side of CE interphase, hydrogen ions will accept two ions and create one hydrogen molecule in gas phase and bubble upon into the CE membrane and migrated toward the inner layer units of the pipelines controlled by Fick's diffusion laws.

[0029]

[0025] The dimensions of the self-propelled cell fuel units are defined as having W in length and H in height and in a special shape that can be integrated into a pipeline as a section of the whole installed pipelines.

[0030]

[0026] In addition, water splitting reaction for production of hydrogen and oxygen has been widely used for de-saltation of sea water, however, the approach proposed here is unique since the oxygen is released to the environmental surroundings like plant breath (102) and only hydrogen was encapsulated inside the pipelines (101) and stored for late usage as final products.

[0031]

[0027] None of steel material is involved as structural members of the pipeline or sealing parts in the structure. Corrosion of pipelines can be avoided to transport hydrogen safely.

[0032]

[0028] The energy driving the water splitting reaction comes from both / either the external electric grid and / or mini energy harvesting and scavenging of the daily cycling thermal heat, moisture, water, and temperature gradients (110 and 111). The fabricated self-healing membranes of concrete pipelines based upon a piezoelectric effect from sintered microcrystalline silica micro / nanoparticles as device for electric generator is further demonstrated in Figure 1 (114). The rectifier 106 in Figure 1 can convert the alternative electricity into direct electricity and initiate the water splitting reaction directly.

[0033]

[0029] In addition, the complex membrane units shown above can be installed as a combined macro / micro cell unit in the underground tunnel or locomotive trains. Alternatively, the design for the whole hydrogen transportation and storage can be separated into two functional sections: 1) oxygen evolution reaction in hydrogen station; 2) hydrogen evolution reaction station lines. Current nano / micro silica sand used in concrete cement or other industries are amorphous. Their piezoelectric effects have been destroyed or weakened due to processing conditions; however, it is anticipated that the sintered microcrystalline silica particles and / or micro / nano sized particles can harvest surrounding soil energy, transferring electron through mechanical stress and resonant oscillation of its quartz crystalline materials in contact with hydrogel of AquluMax™ defined further in detail.

[0034]

[0030] Once the microcrystalline silica particles are subject to mechanical deformation, it will create electric charge. In addition, the plant based nano protein particles encapsulated in the AquluMax™ can potentially initialize the resonant oscillation with a frequency shift (M) harvesting mechanical energy from deformation of concrete like polypeptide of collagen. The mechanical stress generated by flexible self-healing concrete is a natural response to the permeability of concrete pipelines related with surrounding moisture and water intrusion to the pipeline concrete wall. Other piezoelectric or magnetic materials such as ferric metal materials from waste or circular economics can be incorporated into the membranes. It was discovered that copper screen / wire is useful as a current collector. In addition, utilizing the carbon fibers as both reinforced components and current collectors is another alternative raw material.

[0035] DESCRIPTION OF INVENTION IN DETAIL

[0036]

[0031] Background Information

[0037]

[0032] Steel and reinforced plastic composites have been used for transportation and storage hydrogen, the challenging issue in the current hydrogen economics is that hydrogen should be delivered from where it is produced to the point of end users, delivering of hydrogen is still a local, much smaller sized than natural gas (NG) pipeline due to the technical and economic barriers. The range of hydrogen use will depend on various barriers to market adoption, the lack of infrastructure cited as the second selected barrier, and technical advancement fourth. U.S. has approximately 1 ,600 miles of dedicated pipeline for transporting the natural gas. The industrial recommended safe blending dose level of natural gas to hydrogen is more likely less than 20% without explosions. The impurities present in natural gas such as hydrogen sulfide (H2S), oxygen (O2), carbon dioxide (CO2), water (H2O) and in some cases mercuries (Hg) are cited as the most challenging issues.

[0033] The gas of H2S, CO2, and oxygen present in the gas stream through leaks in compressors and surface equipment will cause corrosion to steel pipelines and decompose the polymeric materials of reinforced plastic composites. If free water in the gas stream is not removed, it will lead to hydrate formation along the pipeline. Cavitation occurs when the water molecules are trapped inside the pipeline. To avoid gas hydration, chemical additives with special inhibitors must be added. When CO2 dissolved in water, it will form carbonic acid, resulting in precipitation of CaCOs and creating solid aggregation inside the pipelines. It will affect the surface smoothness of the pipeline and create more flow issues for the gas stream.

[0038]

[0034] Hydrogen sulfide (H2S) also coexists with CO2 in many gas streams and its presence causes severe corrosion since iron can react with both sulfide ion and carbonic ion to precipitate out of the liquid solutions. Hydrogen sulfide is a toxic gas, its leakage is not tolerated. To overcome the corrosion issues of the pipelines, fusion- bonded epoxies (FBE) are the most applied coating for underground steel pipes, however, it is also subject to damage from ultraviolet (uv) rays, special UV protections must be selected. The high purity of hydrogen is manufactured from hydrocarbons converting diesel into 90 % commercially used hydrogen. These impurities, originated from the petroleum refining and tracking operation processes, are hard to eliminate without expensive processes. Electrolysis is the cleanest technology with zero emissions; however, it is also the most expensive with disadvantages of storage and transportation problems. Developing alternative materials and advanced manufacturing technologies for building low-cost infrastructure of hydrogen superhighway is needed.

[0039]

[0035] Currently, hydrogen is stored by three methods: high-pressure gaseous storage, low - temperature liquid, and solid-state hydrogen storage. Solid-state materials are the safest and provide the most hydrogen storage density. Solid-state materials used for hydrogen storage are the same as solid-state battery electrolytes. Nano single layered nanocarbon sheets were prepared for reversible hydrogen storage. Magnesium hydride (MgH2) provides superior storage capacity in a claimed "burst effect". Activated bamboo charcoal with microwave irradiation and KOH activation was used as hydrogen absorbent agents and super-capacitor. Gradual growth of solid electrolyte interphase (SEI) dendrites is a well-known concern in terms of battery service life.

[0040]

[0036] Recently, concrete materials used in salt caverns for hydrogen storage have attracted great attention due to their capabilities of preventing hydrogen from leakage. Hydrogen has been proposed to be stored in bedded salt deposits or hot rock as options by Aramco. Epoxy resin as sealers for salt caverns. So far, only pure form of hydrogen is stored in the underground. Caverns with a high degree of purity are recognized as the most convenient storage sites, however, none of concrete pipelines for both storing and transporting hydrogen simultaneously has been disclosed due to concern on leaking of hydrogen.

[0041]

[0037] The leaking of hydrogen from the storage tankers is a function of the permeability related with the physical adsorption / desorption of moisture and water migration in capillary, and hydrogen molecule's diffusion in the media. It follows the Stokes- Einstein diffusion equation. For hydrogen ion migration in porous system of concrete, the penetration distance of hydrogen ions in water solution into the concrete wall under its own capillary pressure can be calculated with a simplified Washburn's equation.

[0042] DESCRIPTION OF INVENTION IN DETAIL

[0043]

[0038] As shown in Figure 3, when relative humidity (RH) is over 50.0 (%), the relative permeability of oil reduces dramatically. At above 75.0 (%), there will be no oil phase transported in the porous media. Since hydrogen is miscible with oil phase only, not water phase, none of hydrogen molecules can dissolve itself in the water phase. On the other hand, only protons can dissolve in water phase and permeate through the water saturated phase in the form of ions. Quartz or silica sand is hydrophilic in nature. It has microcrystalline structure in bulk and reactive sites on its surface with siloxane group extended in situ, granting its super wetting to proton ions, but impermeable to hydrogen molecules.

[0044]

[0039] Table 1 lists a series of calculated data of hydrogen diffusion constant and liquid wetting relative distance (examples 1 -4). Hydrogen ions in water have a diffusion rate of 1x10-7order (example 1), while in 12.0% salt brine, it has a diffusion constant of 1x10-10(example 3). When 10.0 (%) AquluMaxTMsolution is mixed into 10.0 (%) salt brine, the predicted diffusion constant is 1x10-13(m2 / s) (example 4) and the relative wetting distance reduced by 1 .28 times more than example 3. Listed in examples 7-9 are the measured diffusion constants of API X 80 steel AquluMax™ as potential cross-linking hubs: Laser engraving technology, controlled by advanced digital manufacturing technology, will be a perfectly desirable tool for obtaining the desirable surface texture and specially sized pin holes to achieve the desirable permeability of individual CEM (101), PEM (102), and AEM (103). The electron-spin polyimide nanofibers may be an excellent filtration agent for hydrogen ion. Silica sand as one of the high energy density raw materials for energy storage applications has been studied intensively in the past decade. The degradation of anode solid electrolyte interphases (SEI) due to the expansion of anode Si with Li ion has been identified as potential barriers for the transfer of the battery.

[0045]

[0040] Perceivably, the interface between the steel bar and sulfate ion intrusion due to the cracking of the deformed cement / sandstone is directly accounted for the corrosion of the concrete structure that might create the same SEI issues. As such, carbon fibers or copper rods instead of steel bars should be selected as anode electrode membranes. An addition of grinded microcrystalline silica is believed to be a crucial step for reducing the SEI. Currently, graphite or graphene, silicon, and carbonized bamboo have been tried as anode materials. A well-known reaction of the dissolution of quartz and silica in aqueous solutions occurring is silicic acid.

[0046]

[0041] Recognized as the most cost-effective approach for storing massive quantities of hydrogen, however, the availability of large caverns is out of the question in many places. The pipeline materials proposed here like cavern's are made of grinded quartz and cristobalite bonded by cement and self-healing agent of AquluMax™ solutions. The assembled tunnels and / or extruded pipelines of these materials are functionalized not only as a mini cavern for storing hydrogen, but also manufacturing advanced hydrogen powered by installed batteries from electric grids and self-propelled daily circulated heat flux and surrounded flow of water and moisture through the fabricated concrete wall members. Like growing plants, it releases oxygen daily to the environment and retains hydrogen as fuel for vehicles simultaneously. This will further reduce the unit cost of hydrogen in a long run.

[0042] Current nano / micro silica sand used in concrete cement or other industries are amorphous. The piezoelectric effects have been destroyed and / or weakened due to processing conditions, however, the sintered microcrystalline silica particles and / or micro / nano sized particles can harvest surrounding soil energy that converts cycling strains of concrete and resonant oscillation of quartz molecules in concrete. Once the piezo micro crystalline silica particles are subject to mechanical deformation. It will create electric energy to power water electrolysis reaction. In addition, the plant based nano protein particles encapsulated in the AquluMax™ can initialize the resonant oscillation with a frequency shift (M) that can harvest energy mimicking the polypeptide of collagen.

[0047]

[0043] Hydrogen is not only the cleanest, but also the most expensive of energy transition and decarbonization. The raw materials used in this proposal are silica sand, environmentally friendly, and widely available in the world. The cost of processing these raw materials is 10-20 times less than that of steel and polymeric materials with less carbon footprint toward net-zero of 2050. Since the selected silica undergoes a series of unique cement hydraulic curing reactions, base solution, sodium chloride, water, and moisture are favorable in sintering the silica sand into calcium carbonates through the reaction of dissolved carbon dioxide with calcium ions in water and formation of calcium silicate bonds by Pozzolan reaction.

[0048]

[0044] Especially, the incorporated hydrogel polymers of AquluMax™ potentially provide a unique self-healing flexible cross-linkage by chelating and / or clicking chemistry. Piezoelectric effects of microcrystalline silica would allow the system to harvest the electricity from surrounding soil environment. This is one of the biggest advantages of the proposed projects over current pipeline systems. Carbon dioxide, hydrogen sulfite, and water in the current pipeline transportation of natural gas and hydrogen must be restricted and / or eliminated from the pipeline stream as impurities to prevent the steel pipeline from corrosion, cavitation, and embrittlement, and mitigate the potential risks of explosion due to the hydrogen leaking in reinforced plastic pipelines. These unsolved issues can be avoided with the newly developed pipeline products.

[0049]

[0045] Materials used for preparing anode electrode membrane include a blend of cement, water, and silica typical products including silver 200, frac 100 mesh, and W&W, originally from the trial materials of gMI, LLC. Limestone, AquluMaxTM, Bentonite, ordinary Portland cement (OPC), and Portland cement (PC). Sodium chloride as electrolyte for hydrogen ion transportation in water splitting reaction. The 100mesh frac sand, grinded Silver 200, and Whit&White are conceived to play a critical role in enhancing the piezoelectric effects after being sintered into concrete with their microcrystalline structure. Common concern on the above products is that microcrystalline silica is carcinogenesis and needs special care. All suppliers of these micro-silica sand companies have safe operation procedures in place according to EPA / OSHA rules and regulations, it is also well-known that silica sand could be effectively grinded, and its dust suppressed by 99.0 %.

[0050]

[0046] Intermediate permeable porous solid-state membrane: A blend of activated charcoals with silica particles of different particle sizes will be used to get a controllable transportation of hydrogen ions through the intermediate layer. Optionally, a poly-arylene- N comfortable coating will be used to insulate the surface of the ISSM from AEM and CEM layers while still to allow the hydrogen ion to pass through. Cellulosic acetate and cellulosic filter papers are common raw materials for allowing hydrogen ion passing through while blocking the oxygen and others from passing through.

[0051]

[0047] Materials prepared for cathode electrolysis membrane include microcrystalline silica, magnesium oxide, aluminum oxide, zinc oxide, charcoal, graphite, graphene, and their blends together. Aluminum wire screens and carbon fibers are also potential candidates as cathode materials.

[0052]

[0048] The formula for each designated layer of the prepared layer concrete materials can be evaluated with the following test methods: 1) compressive test per ASTM C 39, 2) cube block test per ASTM C 109, 3) Brazilian splitting tensile test; 4) miniscale home-made of gas permeability; 5) water head permeability test, 6) ion transportation test by monitoring the electric resistance of the tested sample's blocks, 7) voltage of the membranes as a function of time and / or current amperes by voltammetry. The self-healing concrete ingredients will be extruded into solid- state composites for underground / aboveground transportation.

[0053]

[0049] The processing for extruding the unit / cell and parts for anode electrolysis membrane, comprised of: A) microcrystalline silica particles coated with AquluMax™ coatings or blended with AquluMax™, cement, anode micro / nano particles such as copper oxides, zinc oxides, carbon fibers as reinforcement; B) cathodic electrode membrane, comprising of graphite, carbon fibers, activated charcoal, C) intermediate solid-state membrane (ISSM), comprising of special micro-silica, AquluMax™, Whit&White, cement, insulating polymeric coatings, such as polyimide resin, epoxy resin, or novolac epoxy resin for insulating positive and negative charge of cathode and anode; D) channel for storing and transporting the hydrogen gas and ion and generation of hydrogen in which, metal hydride, salts, and water are encapsulated in the confined pipeline's space. Also, the schematic of magnetic disks installed on both sides of the pipelines based upon the magnetron principle was added to enhance the charges with the harvestable energy such as water flow and moisture flow in the channels once the water flows are electrolyzed from the top to the bottom of the storage station and pipelines.

[0054]

[0050] Since partial hydrogen is generated by self-propelling hydrogen generator, the system is an ecofriendly smart system that can be called as pro-active hydrogen storage and transportation system, in which, as shown in Figure 4, the proactive smart hydrogen storage and transportation system includes:

[0055]

[0051] Hydrogen storage membrane - 401

[0056]

[0052] Hydrogen storage chamber - 102

[0057]

[0053] Intermediate layer of HSM - 403

[0058]

[0054] Structure frame support - 404

[0059]

[0055] Wind farmer frame for electricity - 405

[0060]

[0056] Solar power generator - 406

[0061]

[0057] Surrounding carbon block / clay / soil layers - 407

[0062]

[0058] Funnel for wind / rains - 408

[0063]

[0059] Hydraulic pump's - 409

[0064]

[0060] Electrolysis for water splitting system - 410

[0065]

[0061] Electrolysis for oxygen - 411

[0066]

[0062] Pipeline for clean water storage transportation - 412

[0067]

[0063] Energy storage water transportation - 413

[0068]

[0064] Central automatic control unit 414.

[0065] To further demonstrate how the conceptual idea can be realized, examples 18 - 24 list several examples on how to prepare for the cell / unit of hydrogen generation, storage, and transportation pipelines and tunnels.

[0069]

[0066] Example 18 (Notebook ID: 090802023-4): 727.0 (gram) of M3500 (Cristobalite), manufactured by a commercial supplier was weighed in a digital balance having an accuracy of 0.1 (gram), then, blended with 81 .0 (gram) of lime, then, added into a two-gallon sized tanker. After adding 767.0 (gram) of Portland Ordinary Cement (OPC) into the tanker, the whole mixture was fully blended in the tanker for 3 to 5 (minutes). A kitchen blender was used to charge the mixed powder components with 36.6 (gram) of AquluMax™ and 346.0 (gram) of purified water. After blending the mixed components for 3-5 (minutes), a paste was generated. The mixed components were fully blended into a paste. A squared frame was prepared with a copper rod wire as mesh intertwined within in 10 mm in length. The diameter of the copper wire is 0.8 (mm). The cement paste was compressed in the forming box of 120 (mm) x 120 (mm) x 12 (mm) in sized wood frame, then, it was cured in air for 24 hours before the samples were placed in water tanker cured for over 7 days and being cut into squared dimension of 10Ox 100 x 20 (mm). The flat plate made in this way was faced as shaped like the tooth shape as support of item 107 as shown in Figure 1. Simultaneously, the materials were used as the primary materials of piezo effect materials that can generate alternative current.

[0070]

[0067] Example 19: A cylindrical disk having a diameter of 78 (mm) and thickness of 25 (mm) was prepared. The processes for making the disk include: 1) filling the paste materials shown in example 2 into a cylindrical PVC pipeline; 2) tapping the paste materials into packed cylindrical blocks; 3) curing the materials in air over-night in water for 7 days before cutting the tubing materials into disk with a thickness of 25.0 (mm). This form solid state materials were used as the cathode electrolysis membrane of part 101 shown in Figure 1.

[0071]

[0068] Example 20: 24 pieces of hexagon shaped testing samples were prepared using the paste recipes of example 1 . The procedures for creating the test samples include: 1) filling the past materials of example 1 into a silicon molders; 2) tapping the molder to evaluate the bubbles encapsulated in the paste; 3) tapping for at least 5 minutes to make sure the mixed components uniformly distributed to each other; 4) place a 15 (LBS) of weight on the top of the molder; 4) leave the samples overnight (12 hr. or more); 5) release the sample from the molder, 5) place the sample's in water tankers for 1 , 3, 7, 14, 28 days before conducting compressive testing.

[0072]

[0069] Example 21 : (NOTEBOOK ID:09082023-3): 723.0 (gram) of M3500 (Cristobalite), manufactured by a commercial supplier was weighed in a digital balance having an accuracy of 0.1 (gram), then, blended with 81.0 (gram) of lime, then, added into a two- gallon sized tanker. After adding 767.0 (gram) of Portland Ordinary Cement (OPC) into the tanker, 9.0 (gram) of graphite was added into the tanker. The mixture was fully blended in the tanker for 3 to 5 (minutes). A kitchen blender was used to charge the mixed powder components with 36.6 (gram) of AquluMax™ and 346.0 (gram) of purified water. After blending the mixed components for 3-5 (minutes), a paste material was generated.

[0073] A squared frame was prepared with a copper rod wire as a mesh intertwined within the 10 mm in length. The diameter of the copper wire is 0.8 (mm). The four side frames were created with a laminated plate and cross-sectioned with a copper rod wire material as shown in Figure 5. One 120 x 120 (mm) x 25.0 (mm) flat block was prepared by filling the concrete frame plates with the mixed components of example 4, then, the blended paste materials were tapped, consolidated into flatten blocks, and cured overnight, then, placed in water tanker for 7 days before testing the sample's piezoelectric effect. The flattened plates were used as the support part of 108 demonstrated in Figure 1.

[0074]

[0070] Example 22: The cylindrical tube having a dimension of 78 (mm) in diameter and 110 (mm) in height was prepared with the process procedure as: 1 ) filling the paste materials into the cylindrical PVC pipeline; 2) tapping the paste materials into packed test blocks; 3) placing the testing samples in the cylindrical test tube for 7 days before cutting the samples into testing samples; and 4) the samples were downsized into a disk with thickness of 12.0 (mm).

[0075]

[0071] Example 23: 24 pieces of small hexagon blocks were made with a silicon molder. The size of hexagon blocks is shown in Figure 6 and has a height of 20 (mm). The hexagon blocks were placed under compressive strength in a mini-lnstron test machine.

[0076]

[0072] Example 24: Preparation of Permeable electrolyte membrane (PEM). 10 layers of semi- permeable thin cellulose Whitman paper, having a diameter of 100 (mm), was coated with butylene acetate coating, then dried under the sun before being laminated on both sides with 0.8 (mm) of thin copper plates.

[0077]

[0073] Example 25: Compress Test: Samples from examples 1 and 4 are subjected to compressive test after being immersed in the water tanker for 1 , 3, 7, 14, 28 days to evaluate the performance of the mixed components. Table 3 listed the performance of samples of 4" x 4" x" 1" .

[0078]

[0074] Example 26: Piezoelectric Test: As Shown in Figure 6, the assembled units, consisting of both piezoelectric for self-propelling electricity and hydrogen, are tested in a circular electric loop, in which, a digital signal generator generates a designated electrical signal with a defined voltage. The digital signal generator was used to control the electric frequency and voltage of the power source. Response electricity signal of the designated pipeline units was recorded by a multimeter on the top and bottom sections of the tested self-propelling hydrogen pipeline. A plot of electricity voltage vs current characterizes the piezoelectric effect of the assembled cell / units.

[0075] Clearly as shown in Figure 7, the scanning frequency was changed from 1 Hz to 1 .0 million Hz In a squared voltage rate of signals. The cell / unit in low frequency demonstrates a super piezoelectric effect at voltage of 7.5 (v). Furthermore, when the voltage was alternate, LN (measured current) vs. Ln (Voltage) shows straight correlation ship when scanning rate is less than 10,000 (number per second) as shown in Figure 8. This demonstrates that a strong piezoelectric effect exists if the wave frequencies are less than 10,000 (Hz).

[0079] Table 2. Measured Compressive Strength of Pipeline cell / unit

[0080] 1). Number of samples tested per group: 6

[0081] 2). Modified compressive strength tests were used with scale-down size of

[0082]

[0075] The above examples from 1 to 6 and 18 to 26 (excluded examples of 7 to 17) are explanatory for demonstration only. Any change and variation do not mean that it changes the scope of the formed cell / units of pipeline functionalized as a piezoelectric engineered material. Any deviation from the above examples does not exclude the further optimization and in depth exploratory to both the Piezoelectric and hydrogen energy generation. Table 3. Measured Voltage and Current on The Terminals of Self-Propelling Energy Generator, Hydrogen Storage and Transportation at a voltage setting of 7.5 (V) with triangle wavefunctic triangle electronics

Claims

CLAIMSWhat is claimed:[1] A design for a micro / macro pipeline cross sectional cell / unit comprised of functional component:1) self-propelling energy harvesting.2) hydrogen and oxygen generator.3) an electric rectifier.Powered by piezoelectric effect of micro-crystalline silica, semicrystalline silica coated with inspired multifunctional coatings through mechanical, thermal, and solar energy conversion of alternative electricity into direct current, generating hydrogen encompassed inside the pipeline and expelling the oxygen into outside of the pipeline, storing, and transporting the hydrogen useful for the infrastructural construction of hydrogen highways.[2] The design of claim 1 , wherein, the device of the self-propelling energy harvesting consisting of functional components of polysilicon, macro / microcrystalline silica, semi-crystalline silica, amorphous crystalline silica, aluminum silica, aluminum oxide, and other crystalline and semicrystalline materials that can convert the mechanical, thermal, and photos, and others into the electricity with piezo-electric effect plus the concrete cements and aggregates, consolidated together with at least one of the bioinspired multifunctional additives.[3] The design of claim 1 , wherein, the device is composed of at least one of the electrolyzes cell / units, consisting of cathode electrolyte membrane, permeable electrolyte membrane, and anode electrolyte membrane plus at least one of the rectifiers that can convert the harvested alternative electric energy into the direct current by direct connection of the rectifier's wires with current collectors supported by porous diffusion membrane substance.[4] The design of claim 2, wherein, at least one of the crystalline minerals originated from polysilicon and crystalline and semi-crystalline silica sized from0.00001 to 100 (micron) in diameter.[5] The design of claim 4, wherein, the device of cathode electrolyte membrane made of macro / microcrystalline silica, mixed with magnesium oxide, aluminum oxide, and other solid mineral materials, cemented into solid state block / unit, connected with copper rod and / or wires as grid or meshed network.[6] The design of claim 5, wherein, the device of permeable electrolyte membrane consisting of porous sized cellulose acetate, and / or other water swollen types of polymeric hydrogel polymeric materials, only hydrogen ion can pass through the permeable electrolyte membrane.[7] The design of claim 6, wherein, the device of anode electrolyte membrane consisting of at least one of the macro / micro crystalline silica and semi-crystalline silica particles plus graphite, graphene, and / or charcoal carbons, and others.[8] The design of claim 7, wherein, the device of cathode electrolyte membrane, permeable electrolyte membrane, and anode electrolyte membrane coupled together with epoxy or other thermal stable structural glue together to create a central cell / unit that can split water into the hydrogen and oxygen.[9] The design of claim 8, wherein, the driver for water splitting reaction in electrolysis cell / units is the direct current converted by the rectifier powered by the self-propelling energy harvesting supporting parts of macro / micro crystalline silica and polysilicon materials through piezoelectric effect and / or electric grid from other energy resources including renewables and fossil fuels.[10] The design of claim 9, wherein, the renewable's energy resource includes harvesting from daily cycling energy such as wind, thermal, and hydraulic, solar energy, bio-mass conversion, and fossil fuels.[11] The design of claim 10, wherein, the harvesting energy is a self-propelling energy generator originated from the piezoelectric effect of polysilicon, silica, crystalline cellulose, or semicrystalline silica, aluminum oxide, mononitride and southern clays.[12] The design of claim 11 , wherein, the device of self-propelling energygenerator is wired into the electrolysis unit by rectifier through converting the alternating current into direct current.[13] The design of claim 12, wherein, the device of the rectifier comprising of at least four terminals connected through electric full or semi-bridge wired rectifiers connected.[14] The design of claim 13, wherein, the rectifier and / or electric grid is controlled by an eco- automation system that the power, electric current, and voltage are controlled by a central monitoring system.[15] The design of claim 14, wherein, the rectifier is designed in such as a way that can connect each cel l / unit as an independent unit to assembly together to create a pipeline in circular shape and / or rectangular shape in tunnels or channels.[16] The design of claim 15, wherein, the connection of the assembly cell / units is sealed together from hydrogen leaking and oxygen mixed into the pipeline and / or tunnels.[17] The design of claim 16, wherein, the assembled pipelines and / or rectangular tunnels meet all engineered performance as a hydraulic cement concrete product having a compressive strength larger than 4000 (psi).[18] The design of claim 17, wherein, the designated pipeline or tunnel supported by the piezoelectric electric membranes to achieve the designated performance requirements of the infrastructural integration.[19] The design of claim 18, wherein, the compressive strength of the pipeline products has a measured value larger than 3000 (psi) per ASTM C30 testing standard.[20] The design of claim 19, wherein, the number of the tested pipeline cell / unit scan number under the standard testing procedure larger than 10,000 before it has a maximum resistance to the current.

Images