EP3966180A1 - Biozement und selbstheilende biobetonzusammensetzungen - Google Patents
Biozement und selbstheilende biobetonzusammensetzungenInfo
- Publication number
- EP3966180A1 EP3966180A1 EP20728123.9A EP20728123A EP3966180A1 EP 3966180 A1 EP3966180 A1 EP 3966180A1 EP 20728123 A EP20728123 A EP 20728123A EP 3966180 A1 EP3966180 A1 EP 3966180A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bioproduct
- concrete
- biocement
- shewanella
- healing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
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- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
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- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0001—Living organisms, e.g. microorganisms, or enzymes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/60—Agents for protection against chemical, physical or biological attack
- C04B2103/61—Corrosion inhibitors
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/26—Corrosion of reinforcement resistance
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Definitions
- the present invention relates to a bioproduct, biocement compositions comprising the bioproduct, methods of their manufacture, bioconcrete compositions comprising the biocement and methods of their manufacture, the invention also includes methods of, and uses for, the bioproduct, biocement and bioconcrete compositions and products, especially but not exclusively, in the control, prevention or repair of corrosion in reinforced concrete structures.
- Cement is a binder, a substance used for construction that sets, hardens, and adheres to other materials to bind them together. Cement is seldom used on its own, but rather to bind sand and gravel (aggregate) together. Cement mixed with fine aggregate produces grout and mortar for masonry, or with sand and gravel, produces concrete.
- Concrete is one of the most used construction materials worldwide as it is strong and relatively cheap.
- Current design for durability is through prescriptive guidance and includes factors such as the disposition of reinforcement to control cracking and crack widths, thickness of concrete cover to reinforcement, quality of concrete and management of water.
- concrete is subjected to a number of degradation processes which hamper the structure to reach its required service life.
- Problems caused by the corrosion of reinforcement in deteriorating concrete structures are widely encountered and are recognized as a major limitation upon the durability of many existing structures.
- the primary reason for premature corrosion is crack formation in the concrete cover. Larger cracks as well as a network of finer cracks allow water, oxygen, chloride, and other aggressive corroding substances to penetrate the concrete matrix to reach the reinforcement.
- Metal chelating agents are produced by a variety of microorganisms, including Streptomyces, Nocardia, Micromonospora, Arthrobacter, Chromobacterium, Pseudomonas, Escherichia coli, Salmonella typhimurium, Geobacter, Shewanella and some nitrogen-fixing bacteria such as Klebsiella pneumoniae and Klebsiella terrigena.
- Shewanella is the sole genus included in the marine bacteria family Shewanellaceae and are found in extreme aquatic habitats where the temperature is very low and the pressure is very high. Shewanella are heterotrophic facultative anaerobes. This means that, in the absence of oxygen, members of this genus possess capabilities allowing the use of a variety of other electron acceptors for respiration, for example thiosulfate, sulfite, elemental sulfur, fumarate, nitrate, nitrite and arsenic in addition to a wide range of metal species, including manganese, chromium, uranium and iron.
- Shewanella The metal-reducing capabilities of Shewanella can potentially be applied to bioremediation of metal-contaminated groundwater, its ability to decrease toxicity of various substances has hitherto made Shewanella a useful tool in bioremediation.
- Some other examples of facultatively anaerobic bacteria are Staphylococcus spp., Streptococcus spp., Escherichia coli, Salmonella and Listeria spp.
- a bioproduct comprising Shewanella for use in preventing and/or repairing corrosion in concrete.
- the Shewanella is selected from the group comprising S. abyssi, S. aestuarii, S. algae, S. algicola, S. algidipiscicola, S. amazonensis, S. aquimarina, S. arctica, S. atlantica, S. baltica, S. basaltis, S. benthica, S. canadensis, S. chilikensis, S. colwelliana, S. corallii, S. decolorationis, S. denitrificans, S. dokdonensis, S. donghaensis, S. fidelis, S. fodinae, S. frigidimarina, S. gaetbuli, S.
- pealeana S. piezotolerans, S. pneumatophor, S. profunda, S. psychrophila, S. putrefaciens, S. sairae, S. schegeliana, S. sediminis, S. seohaensis, S. spongiae, S. surugensis, S. upenei, S. vesiculosa, S. violacea, S. waksmanii, S. woodyi and S. xiamenensis.
- the bioproduct comprises at least one strain of Shewanella and at least one other bacteria species/strain that is non-pathogenic or substantially non-pathogenic.
- the at least one other bacteria species/strain is selected from the group comprising Streptomyces, Nocardia, Micromonospora, Arthrobacter, Chromobacterium, Pseudomonas, Escherichia coli, Salmonella typhimurium, Geobacter, Raoultella terrigena, Staphylococcus spp., Escherichia coli and Salmonella or any other substantially non-pathogenic species/strain of bacteria.
- the at least one strain of Shewanella is S. oneidensis.
- the bioproduct is fluidic and is the form of a liquid, solution, powder, residue, gel, granule, particulate, pellet, microsphere or the like.
- the bacteria of the bioproduct are uncapsulated.
- a biocement having mixed or embedded therein, a bioproduct comprising Shewanella, the cement being for use in preventing and/or repairing corrosion in concrete.
- a method of manufacturing the biocement of the present invention comprising providing a cement base including mixed or embedded therein, a proportion of biproduct the bioproduct comprising at least one strain of a Shewanella bacterium, the bacterium being added when in its dormant state.
- a self-healing bioconcrete comprising:
- the bioconcrete comprises iron in the form of rods, bars, rebars, mesh, filings or powder.
- the bioconcrete additionally comprises a superplacticizer in the region of up to 0.002 % / m 3 of a superplasticizer. It will be appreciated that preferred features ascribed to one aspect of the invention applies mutatis mutandis to each and every aspect of the invention.
- Figure 1 shows Pourbaix diagram for Fe-H20 at 25 °C hatch area shows the pH and potential region of steel in concrete [https://doi.org/10.1016/B978-1-78242-381-2.00002-X]
- Figure 2 shows a bar chart of compressive strength (MPa) for concrete type CEMI and CEMIII with and without bioproduct, tested at 28 days.
- Figure 3 shows water absorption (Kg/m 2 ) via capillary for concrete types concrete type CEMI and CEMI 11 with and without bioproduct, tested at 28 days and for 2 weeks.
- Figure 4 shows water absorption (Kg/m 2 ) via capillary for concrete types concrete type CEMI and CEMIII with and without bioproduct, tested at 28 days and during the first day.
- Figure 5 shows non-steady state migration coefficient (x 10 12 m 2 /s) for concrete types concrete type CEMI and CEMIII with and without bioproduct during the first 200 days.
- Figure 8 shows the ratio of non-steady state migration coefficient for concrete types concrete type CEMI and CEMIII with and without bioproduct, in comparison to reference one (CEMI and CEMIII at 28 days).
- Figure 7 shows analysis of the microstructure via scanning electron microscope (SEM) at 28 days for CEMIII without bioproduct ( Figure 7A) and for CEMIII with bioproduct ( Figure 7B).
- Figure 8 shows surface electrical resistivity (kQ cm) of hardened concrete samples CEMIII with and without self-healing behaviour (Figure 8A) and CEMI with and without self-healing behaviour (Figure 8B), tested from 28 days until 115 days.
- Figure 9 shows superficial electrical resistivity (kQ cm) in a propagation test measured during electrical current injection in the rebars to accelerate corrosion for concrete types concrete type CEMI and CEMIII with and without bioproduct.
- Figure 10 shows cement after the propagation test
- Figure 10A shows CEMI without bioproduct
- Figure 10B shows CEMI with bioproduct
- Figure 10C shows CEMIII with bioproduct
- Figure 10D shows CEMIII with bioproduct.
- references herein to a“fluid” or“fluidic” is intended to encompass any substance or material that possess the capability to flow easily and includes liquids, solutions, powders, residues, gels, granules, particulates, pellets, microspheres and the like.
- Reference herein to“bioactive” is intended to encompass any substance that is capable of eliciting a biological effect.
- Reference herein to a“bioproduct” refers to any substance of matter that comprises bioactive agent(s) in particular, bioactive agents(s) that is/are capable of reducing iron (III) oxide [Fe2C>3] by iron oxide precipitation (MNP).
- the bioproduct of the present invention comprises“bacterial material” and may also refer to a combination of bacterial materials, such as a combination of two or more of the bacterium, a lyophilized bacterium and the bacterial spore of the bacterium.
- the term “bacterial material” may alternatively or in addition also refer to a combination of two or more different types of bacteria, such as two or more Shewanella and other bacteria that are capable of reducing iron (III) oxide [Fe2C>3] by iron oxide precipitation (MNP), such as and without limitation Streptomyces, Nocardia, Micromonospora, Arthrobacter, Chromobacterium, Pseudomonas, Escherichia coli, Salmonella typhimurium, Geobacter and Raoultella terrigena.
- MNP iron oxide precipitation
- a“biocement” refers to fluidic cement, mortar or grout that includes the bioproduct of the present invention and is capable of reducing iron (III) oxide [Fe2C>3] by iron oxide precipitation (MNP).
- references herein to a“bioconcrete” refers to a self-healing hardened material suitable for use in the construction industry and comprising aggregates bonded together by biocement and water.
- Reference herein to“dormant” or“dormancy” refers to the bacterial material being in a state of having normal physical functions suspended or slowed down for a period of time; in or as if in a deep sleep.
- This present invention relates generally to cement compositions including the bioproduct and processes for producing the same, and more particularly cement including bioproduct for controlling corrosion reaction in concrete which includes the cement as a component.
- Concrete is a conglomerate of aggregate (such as gravel, sand, and/or crushed stone), water, and hydraulic cement (such as Portland cement), as well as other components and/or additives. Concrete is generally fluidic when it is first made, enabling it to be poured or placed into shapes, and then later hardens, and is never again fluidic.
- aggregate such as gravel, sand, and/or crushed stone
- hydraulic cement such as Portland cement
- compositions of the present invention offer a more economic and environmentally friendly approach to the production of cement and self-healing concrete and a biofilm that includes non-encapsulated iron reducing bacteria, such as non-encapsulated Shewanella oneidensis cells.
- the compositions and products of the present invention can provide a resistance mechanism to reinforced steel corrosion.
- the use of iron containing waste in cement and concrete production can provide a substrate for the growth of the bacteria which precipitate iron oxide (MNP) and acts to strengthen the concrete.
- MNP precipitate iron oxide
- iron-respiring bacteria and iron oxide materials are mixed with CEMI to form cement, which enables the cement thus produced to inhibit corrosion reaction in concrete, grout and mortars made with the cement.
- compositions of the present invention highlight the potential of microbially induced iron-oxide precipitation (MNP), to work as a corrosion inhibitor, thereby increasing RC service life.
- MNP microbially induced iron-oxide precipitation
- the present invention takes advantage of iron oxide and MNP leading to self-healing bioconcretes with higher strength and durability.
- the concrete compositions of the present invention generally include cement, aggregate, and water.
- the cement is present in the fluid concrete mixture in an amount between about 5% to about 20% by weight based on the total weight of the concrete mixture.
- Aggregates can include, but are not limited to, natural and crushed quarried aggregate, sand, recycled concrete aggregate, blended agro-industry ashes, and the like, as well as mixtures thereof. Aggregate is present in the fluid concrete mixture in an amount around 50% by weight, based on the total weight of the concrete mixture.
- the fluid concrete mixture also includes water, in an amount ranging from about 2% to about 10% by weight based on the total weight of the mixture.
- the fluid concrete mixture also can include other materials as known in the art for imparting various properties to concrete, including, but not limited to, air-entraining admixtures, water reducing admixtures, accelerating admixtures, pozzolans, such as, but not limited to, fly ash, metakaolin, and silica fume, and the like. These agents can be present in conventional amounts.
- the present invention also includes mortar compositions, which generally are similar in composition to concrete, except that mortar is typically made with sand as the sole aggregate, in contrast to concrete which includes larger aggregates. Sand in this sense is aggregate of 3/8 inch and smaller diameter.
- the present application describes a concrete comprising, by mass per cubic meter of concrete, the following components:
- MRD maximum recovery diluent
- oneidensis MR-1) was assessed from an agar plate, and thus, the concentration was 2.3x 10 8 Colony Forming Unit per ml (cfu/ml), of bioproduct produced meaning a colony final concentration between 10 4 and 10 5 (cfu/ml) in the concrete.
- Agar plates were prepared according to manufacturer’s instructions prior to sterilisation at 121° C for 15 minutes .
- Tryptic Soy Broth is the nutritious medium used to support the growth of a wide variety of microorganisms, especially common aerobic.
- the liquid medium recommended for use in qualitative procedures for isolation and cultivation of a wide variety of microorganisms. Hence, the medium was prepared according to manufacturer’s instructions prior to sterilisation at 121° C for 15 minutes.
- the colonies were collected from the incubated plates for the serial dilution of original S. oneidensis strain culture (0.1 ml) and kept in sealed vials containing sterile 9.9 ml MRD. Through carrying that process, very high concentrated S. oneidensi inoculum was achieved and stored in the freezer. The bacteria were defrosted when they were required for cultivation in order to be mixed with concrete.
- the cells of S. oneidensis were grown from high concentrated inoculum once again.
- a 500ml of TSB sterilized in four conical flasks each one was containing 125ml, then 400mI of high concentrated S. oneidensis inoculum were added to individual flasks by pipette. Then the flasks were incubated for three days at 30°C, at 150rpm. Through the serial dilution, the growth measurement of the new culture was checked and the concentration measured was 1.7 x 10 8 cfu/ml. Therefore, the new culture was found to be more concentrated than the original culture.
- the second 500ml of S. oneidensis cells were grown again from the same inoculum as described above. More concentrated S. oneidensis cells were obtained (8 x 10 9 ).
- Another 500ml of S. oneidensis cells were grown from different inoculum at temperature 30°C and speed 200rpm. At this time, bigger flasks were placed in Benchtop Shaking Incubator for almost 19 hours, from that the best concentration of S. oneidensis was achieved 1 * 10 10 . Therefore, to control the concentration, it is preferred to use the same procedure each time and, while the flasks are placed in the Benchtop Shaking Incubator, it is recommended to check the concentration of the bacteria by measuring the optical density.
- Figure 2 shows the average compressive strength results for concrete types CEMI and CEMIII both with and without bioproduct, at 28 days. Data shows that the self-healing behaviour in concrete type CEMIII+BIO surprisingly enhances the compressive strength in comparison to CEMIII without the bioproduct, whereas addition of the bioproduct decreases the compressive strength of concrete made with CEMI by about 5%.
- the performance of concrete was quantified in terms of durability, as regards corrosion of steel reinforcement, with and without the presence of self-healing behaviour.
- the chloride migration coefficient for each concrete composition was determined by the NT BUILD 492 method and is a measure of the resistance of the tested material to chloride penetration.
- the experimental procedure for the determination of the coefficient of migration followed the rapid non-steady state chloride test (NT Build 492, 1999), which included cylindrical specimens with 100 mm diameter and 50 mm of thickness. The specimens were subjected to 14 days of drying at 20°C and 50% of RH before being in a low pressure hermetic recipient and immersed in a solution of calcium hydroxide for vacuum treatment.
- Figure 5 shows chloride migration results for concrete type CEMI and CEMIII with and without bio-product during the first 200 days.
- Figure 8 shows the surface electrical resistivity of hardened concrete samples CEM III with and without self-healing behaviour (Figure 8A) and CEMI with and without self-healing behaviour (Figure 8B), tested from 28 days until 1 15 days. Results show that self-healing concrete tends to increase the electrical resistivity, contributing to a decrease of the chloride ion penetrability in the concrete, thus decreasing the corrosion risk. 120 days after concrete samples were produced, the samples were exposed to electrical current injection in the rebars to accelerate corrosion (called the“propagation test”), superficial electrical resistivity was measured during this entire test.
- Figure 10 shows images of cement types after the propagation test
- Figure 10A shows CEMI without bioproduct
- Figure 10B shows CEMI with bioproduct
- Figure 10C shows CEMIII without bioproduct
- Figure 10D shows CEMIII with bioproduct.
- Substantial cracks, size (0.4mm) after 1 1 days were observed in the concrete CEMI without the bioproduct.
- the decrease in CEMIII +BIO seems to be 10x lower than the decrease observed for concrete without the bioproduct and when compared with CEMI+BIO.
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