WO2013096990A1 - Ciment et béton renforcés a l'oxyde de graphène - Google Patents

Ciment et béton renforcés a l'oxyde de graphène Download PDF

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Publication number
WO2013096990A1
WO2013096990A1 PCT/AU2012/001582 AU2012001582W WO2013096990A1 WO 2013096990 A1 WO2013096990 A1 WO 2013096990A1 AU 2012001582 W AU2012001582 W AU 2012001582W WO 2013096990 A1 WO2013096990 A1 WO 2013096990A1
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graphene oxide
cement
matrix material
cementitious
matrix
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PCT/AU2012/001582
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English (en)
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Zhu Pan
Wenhui DUAN
Dan Li
Frank Collins
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Monash University
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    • 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
    • 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
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/022—Carbon
    • C04B14/024—Graphite
    • 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
    • C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material

Definitions

  • the present invention relates to compositions comprising cementitious material, liquid and substantially uniformly dispersed graphene oxide as well as to matrix materials formed by curing therefrom that exhibit improved compressive and flexural strength relative to equivalent non-graphene oxide comprising matrix materials.
  • the invention also relates to methods of producing such compositions and matrix materials.
  • Ordinary Portland cement is extensively used worldwide for building and construction. However it has limited structural applications without the use of reinforcement due to poor tensile strength and strain capacity. The weak tensile strength is associated with pre-existing flaws. By incorporating steel reinforcing bars and fibres, it is possible to delay the development of microcracks and therefore improve resistance to tensile stresses.
  • Nano-reinforcements in cementitious matrix materials are more effective than conventional steel bar/fibre reinforcements (at millimeter scale) because they can control nano-size cracks (at the initiation stage) before they develop into micro-size cracks.
  • improved mechanical performance by introduction of nano-silica in cement matrix has been reported [1]
  • Nano-silica has a spherical shape (low-aspect-ratio) with diameters less than 30 nm and with a specific surface area of 300m 2 /g.
  • nano-silica can promote cement hydration due to its high specific surface area.
  • nano-silica can highly density the microstructure because the size of nano-silica is comparable to that of gel pore in cement matrix.
  • nano-silica lacks the ability to arrest microcracks derived from nano-size cracks, thus providing little improvement in post peak toughness.
  • CNTs Compared to nano-silica's spherical shape, carbon nanotubes (CNTs) can be regarded as a one dimensional tube (high-aspect-ratio). Depending on whether they are single walled CNTs (SWCNTs) or multi-walled CNTs (MWCNTs), CNTs generally have the diameter of 1-3 nm or 5-50 nm, respectively. The length of CNTs can be up to centimeters, which gives an aspect ratio exceeding 1000. CNTs also exhibit extraordinary strength with moduli of elasticity on the order of TPa and tensile strength in the range of GPa. With the concurrent benefits of high aspect ratio and excellent mechanical performance, CNTs have been found to improve the toughness and strength of cementitious matrix materials.
  • a CNT can be thought of as a graphene sheet that has been rolled up into a tube structure.
  • the tube-shaped CNTs exhibit reduced interfacial contact area since the outermost CNT shields the tubes' internal surfaces from the matrix [14].
  • the lack of interfacial areas between CNTs and the cement matrix deteriorates CNT's reinforcing efficiency, even though CNTs exhibit excellent mechanical properties.
  • MWCNTs introduced as a water suspension with added surfactant admixture did not increase the compressive and flexiiral strength, even though good dispersion was obtained.
  • One of the possible reasons is that the bonding between the MWCNTs and the cement matrix to be rather weak. As a result the MWCNTs are easily pulled from the matrix when subjected to tensile stresses.
  • graphene Similar to CNTs, graphene also comprises sp 2 -bonded carbon atoms [3], providing graphene with excellent mechanical properties. The intrinsic strength and Young's modulus are estimated to vary between 60-130 GPa and 1 TPa, respectively [4].
  • graphene is a flat sheet of carbon atoms with only one atom thickness [5], The planar structure of graphene sheets creates significant contact area with the host material because both the top and bottom surfaces of a graphene sheet are in close contact with the host material.
  • the aspect ratio of a single graphene sheet can reach more than 2000 and value of surface area of a single graphene sheet can theoretically reach 2600 m 2 /g, which are much higher than those of CNTs [6].
  • graphene oxide comprises a mono-layer of sp 2 -hybridized carbon atoms derivatized by a mixture of carboxyl, hydroxyl and epoxy functionalities [7].
  • GO oxygen functional groups, attached on the basal planes and edges of GO sheets, significantly alter the van der Waals interactions between the GO sheets and therefore improve their dispersion in water [8].
  • GO also exhibits high values of tensile strength, aspect ratio and large surface area [9].
  • GO can be easily acquired from natural graphite flakes (inexpensive source) by strong oxidation and subsequent exfoliation.
  • United States patent publication 2011/0210282 to Foley relates to materials comprising a nanoscale material having desirable qualities and a second nanoscale material that provides a dispersant, surfactant or stabilising molecule action.
  • graphene oxide is referred to as one of many possible nanoscale materials having desirable properties that can be incorporated into a bulk material, the document does not comprehend the adoption of such nanoscale materials without the additional inclusion of a further nanoscale material that provides a dispersant, surfactant or stabilising molecule action.
  • Singh et /[10] is directed to composite materials useful for providing electromagnetic interference shielding. While the general focus of this paper is upon graphene oxide/ferrofluid cement composites that demonstrate the desired electromagnetic interference shielding capability there is also passing reference to compositions of cement and graphene oxide prepared using water and having weight ratios of cement to graphene oxide of 1 :0.1 , 1 :0.2 and 1 :0.3, which are equivalent to 10%, 20% and 30% by weight of graphene oxide to cement. The only information regarding mechanical properties of the cement/graphene oxide composites disclosed is limited data relating to Shore D hardness.
  • the present inventors have determined that graphene oxide sheets can be readily dispersed throughout cementitious material pastes such that the cementitious matrix formed upon curing exhibits significantly improved mechanical qualities compared to an equivalent cementitious material matrix that does not include graphene oxide. Importantly, a substantially uniform dispersion of graphene oxide sheets throughout the paste and the matrix material derived therefrom is able to be obtained without the adoption of separate dispersant, surfactant or stabilising agents.
  • the inventors have determined that significant improvements in compressive and flexural strength of the matrix materials produced according to the invention can be achieved with the inclusion of relatively low weight percentage levels of graphene oxide, such as between 0.01% to 0.5% by weight of the cementitious material.
  • cementitious paste compositions and the matrix materials formed therefrom according to the invention may offer a number of significant advantages such as the ability to improve matrix durability, to- reduce the quantity of steel reinforcement required in cementitious matrix structures and thereby allow adoption of thinner and lighter concrete structures, allowing for new architectural designs, reduced concrete consumption and improved environmental sustainability.
  • durability of the matrix materials of the invention may be improved due to the reduced need for adoption of corrosive steel (particularly for marine or aquatic applications) and due to enhanced porosity resulting from GO particles acting as nucleation agents for OPC hydration.
  • composition comprising cementitious material, liquid and substantially uniformly dispersed graphene oxide without the separate inclusion of dispersant, surfactant or stabilizing agents, which upon curing forms a matrix material that exhibits improved compressive and flexural strength relative to an equivalent non-graphene oxide comprising matrix material.
  • a matrix material formed from cementitious material and substantially uniformly dispersed graphene oxide without the separate inclusion of dispersant, surfactant or stabilizing agents, wherein said matrix material exhibits improved compressive and flexural strength relative to an equivalent non-graphene oxide comprising matrix material.
  • a method of producing a composition comprising cementitious material, liquid and substantially uniformly dispersed graphene oxide, which comprises the steps of dispersing graphene oxide sheets within the liquid to form a dispersion without the separate inclusion of dispersant, surfactant or stabilizing agents and mixing the dispersion with cementitious material to form a paste which upon curing forms a matrix material that exhibits improved compressive and flexural strength relative to an equivalent non-graphene oxide comprising matrix material.
  • a method of producing a matrix material which comprises the steps of dispersing graphene oxide sheets within a liquid to form a dispersion without the separate inclusion of dispersant, surfactant or stabilizing agents, mixing the dispersion with cementitious material to form a paste and allowing the paste to cure to form a matrix material that exhibits improved compressive and flexural strength relative to an equivalent rion-graphene oxide comprising matrix material.
  • the cementitious material comprises Ordinary Portland Cement (OPC) and the liquid comprises water.
  • OPC Ordinary Portland Cement
  • Fig. 1(a) shows a SEM image of GO sheets monolayer on a silicon substrate
  • Fig. 1(b) shows a TEM image of GO sheets deposited onto a lacy carbon support film, the observed ridge or crease demonstrate a wrinkled surface texture of GO sheets.
  • Fig. 2 shows the spread area of fresh pastes. The outlines of the area were artificially traced with thick solid lines.
  • Fig. 3(a) shows the effect of age on compressive strength; and Fig 3(b) shows the standard deviation of compressive strength results measured at various ages.
  • Fig 4(a) shows stress-strain curves under compression
  • Fig. 4(b) shows load- displacement curves under tension.
  • Fig. 5(a) shows a SEM image of plain paste showing a straight-through type crack (arrow); and Fig.5(b) shows a SEM image of GO/cement composite showing a number of fine cracks (arrows) with few branches.
  • Fig. 6 shows a reaction scheme between carboxylic acid groups and hydrated production [Ca(OH) 2 and C-S-H] of cement.
  • compositions of the invention comprising cementitious material, liquid and graphene oxide.
  • the compositions of the invention generally take the form of what is known in the industry as cementitious pastes, usually having the consistency of a paste or slurry, depending upon the extent to which liquid has been included.
  • the compositions according to the invention will solidify and harden due to a chemical process taking place, involving the liquid, where bonds are formed between components of the composition. Where the liquid comprises water this process is known as hydration.
  • the hardened or cured material is referred to generally as cementitious matrix material, matrix material or concrete.
  • cementitious materials are known and extensively used to form matrix materials with applications in buildings, roads, bridges, surfaces and pavements, airport runways, dam walls, retaining walls, railway sleepers, pipes, precast elements such as for commercial and residential buildings, cladding, mortar, render, marine and aquatic structures and the like.
  • the most extensively used cementitious material is Portland Cement or Ordinary Portland Cement (OPC), although other agents, when mixed with a binder liquid such as water, also exhibit cementitious properties of forming chemical bonds and hardening to give rise to a concrete-like matrix material.
  • POC Ordinary Portland Cement
  • examples of other cementitious materials include ground granulated blast furnace slag (GGBFS), some forms of fly ash, such as class C fly ash, ground limestone and silica fume.
  • cementitious agents may be used in compositions of the invention either individually or in combination, most usually in combination with Portland Cement.
  • a variety of different forms of cement are routinely produced depending upon the desired qualities. Some examples include Portland Cement types I, II, III, IV and V, Portland blast-furnace slag cement, Portland- pozzolans cement, Pozzolans-modified Portland Cement, slag cement, slag-modified Portland Cement, expansive cement, white cement, water-repellent cement, masonry cement, mortar cement, oil well cement, plastic cement and rapid setting cements.
  • cementitious materials compositions of the invention may also include other additives. It is conventional for aggregates such as sand, gravel or stones to be included within cementitious compositions.
  • Pozzolans such as volcanic glass, zeolitic trass or tuffs, rice husk ash, diatomaceous earth and other natural pozzolans are often included in cementitious compositions, as although they are not cementitious per se, they improve the cementitious qualities of other cementitious agents.
  • a range of other additives such as plasticisers, superplasticisers, pigments accelerators, such as calcium chloride and the like can also be included within cementitious compositions according to the invention.
  • Other agents that may impart desirable properties upon the compositions of the invention and the matrix materials formed therefrom include solid particles or powders, such as of electrically conductive material such as manganese oxide, tin oxide, titanium oxide and/or nickel oxide, or semi-conductive material including semiconducting nanoparticles such as CdS, PdS, CdSe, or resistive material, magnetically active material, carbon nanotubes, quantum dots, nanowires or other fine threads or fibres, ceramics, metals including metal nanoparticles such as.
  • the liquid included in the compositions of the invention will depend upon the cementitious material or materials selected, and can be an organic or aqueous liquid. In many embodiments, particularly when the cementitious material comprises Portland cement the liquid will comprise ' water.
  • organic liquids include ethanol, methanol, toluene, ethylene glycol, DMF and THF.
  • the cementitious paste compositions and matrix materials of the invention are characterised by having GO sheets substantially uniformly dispersed throughout so that the sheets are for the most part relatively evenly distributed through the composition or matrix, assuming that the composition or paste is adequately mixed during production.
  • the generally uniform distribution of GO throughout the compositions and matrix materials of the invention can readily be determined by analytical techniques such as Transmission Electron Microscopy (TEM).
  • the inventors have shown that due to the hydrophilic character of GO it is able to be readily dispersed within a polar binding liquid such as water, without the need for the addition of surface active agents such as dispersants, surfactants or stabilizing agents. While other components of cementitious compositions such as ' components of the cementitious materials themselves or additives such as pigments, plasticizers etc. may exhibit some surface activity it will be understood that in a preferred aspect of the invention agents are not separately included in order to act as dispersants, surfactants or stabilizers. Agents with surface activity are preferably only to be included in the compositions where their primary function in the composition is other than as a dispersant, surfactant or stabilizer.
  • a dispersant or a dispersing agent is a surface-active substance added to a suspension, usually a colloid, to improve the separation of particles and to prevent settling or clumping.
  • Dispersants are normally made up of one or more surfactants but may also be gases.
  • a surfactant is an amphiphilic substance that can absorb on interfaces and lower the surface or interfacial tension.
  • Stabilizing molecules are agents that function to stabilize nanoparticles in suspension or dispersions and can be chemically or physically bound to the nanoparticles being stabilized, thereby eliminating problems that occur due to lack of solubility, reagglomeration, migration, or volatility.
  • GO sheets are readily commercially available and can be produced by the process referred to as "chemical exfoliation” from graphite, as outlined in detail in Hummers and Offeman [12].
  • a slightly modified “Hummers” process is often adopted, which involves addition of concentrated sulphuric acid into a flask filled with graphite at room temperature; cooling the flask to 0 °C in ah ice bath, followed by slow addition of potassium permanganate; the flask is then allowed to warm to room temperature before it is raised to 35 °C in a water bath, and the mixture is stirred with a Teflon coated magnetic stirring bar for 2 h; the reaction mixture is then cooled in an ice bath, followed by the addition of distilled water in excess to the mixture; Hydrogen peroxide (30 wt % in water) is then added until gas evolution ceases and the resultant brown yellowish suspension is intensively washed by filtration, first with a diluted solution of hydrogen chloride (0.1 M) and then with distilled water,
  • the matrix materials produced according to the invention exhibit significantly improve mechanical properties in comparison to matrix materials that are in all other respects that same but for the exclusion of GO.
  • significant improvements in compressive and flexural strength of the matrix materials produced according to the invention have been demonstrated with the inclusion of relatively low weight percentage levels of graphene oxide, such as from about 0.01% to about 0.5%, from about 0.02% to about 0.2%, from about 0.03% to about 0.1% or about 0.05% by weight of the cementitious material.
  • Compressive and flexural strength are well understood mechanical properties that can readily be measured by standard techniques. Flexural strength is one measure of the tensile strength of cementitious materials and is routinely determined by measuring the bending force that a beam or slab is able to resist before failure. For example, a 3-point bending test can be conducted. Compressive strength can be determined by measuring the compressive force that a sample of material can withstand before failure and this test may be conducted using readily available compressive strength testing apparatus.
  • Matrix materials produced according to the invention may demonstrate improved compressive strength in comparison to that of an equivalent matrix material that does not include GO of at least about 15%, such as at least about 18%, about 20%, 22% or 24%. Similarly, matrix materials produced according to the invention may demonstrate improved flexural strength in comparison to that of an equivalent matrix material that does not include GO of at least about 30%, such as at least about 35%, about 40%, 45% or 50%.
  • Matrix materials produced according to the invention can include aggregates and other optional additives to form concretes.
  • a range of concretes such as high-performance concrete, structural lightweight concrete, insulating and moderate-strength lightweight concrete, autoclaved cellular concrete, high-density concrete, mass concrete, preplaced aggregate concrete, no-slump concrete, roller-compacted concrete, soil-cement, shotcrete, shrinkage-compensating concrete, pervious concrete, white and coloured concrete, polymer concrete and ferrocement are included within the matrix materials according to the invention.
  • the present invention also includes methods of producing a composition comprising cementitious material, liquid and substantially uniformly dispersed graphene oxide as well as to methods of producing the matrix materials produced therefrom.
  • compositions of the invention comprise the steps of dispersing graphene oxide sheets within the liquid to form a dispersion without the separate inclusion of dispersant, surfactant or stabilizing agents and mixing the dispersion with cementitious material to form a paste, which upon curing forms a matrix material.
  • the matrix material can be produced in the same manner, but with the additional step of curing the composition.
  • compositions of the invention can also be produced in other means such as by including GO at the time of mixing the cementitious material, liquid and optional other ingredients such as aggregate and other conventional additives.
  • Matrix materials produced according to the invention can be produced on an industrial scale according to processes similar to that outlined in the laboratory scale process detailed in the example section that follows. The performance of matrix materials can be influenced by the mixing procedure used in industrial scale. The mixing procedure includes the type of mixer, the order of introduction of the materials into the mixer, and the energy of mixing (duration and power).
  • the mixing procedure best suited for producing matrix materials will be selected according to the specific performance requirements of the product. In many cases, however, it will be desirable to ensure homogeneity of the materials after mixing and placement. Determining the quality of the materials mixed is referred to as the measurement of the efficiency of the mixer.
  • the efficiency of the mixer will impact upon distribution of cement content, variations in compressive strength and variations in consistency as measured by the slump test, which will improve with increased mixing time.
  • the OPC is provided by Cement Australia, West Footscray, and conforms to the requirements of Type GP - General Purpose Cement, as defined by the AS 3972-2010.
  • Graphite, with an average particle size of 44 ⁇ was obtained from Zhongtian Co. Ltd. (Qingdao, China). According to Li et al. [11], the synthesis of GO dispersions is described in the following section.
  • Graphite oxide was synthesized from natural graphite using the modified Hummers method [12].
  • the graphite powder (10 g) was added to an 80 °C solution of concentrated H2SO4 (60 ml), K 2 S 2 0g (5 g) and P2O5 (5 g).
  • the resulting mixture was cooled to room temperature over a period of 6 h, then carefully diluted with water, filtered, and washed until the pH of the filtrate was close to 7 (Milli-Q® water was used in all experiments).
  • the peroxidized product was dried in 50 °C oven overnight, and placed into cold (0 °C) concentrated H 2 S0 4 (230 ml).
  • the water-to-cement ratio of all mixtures was kept at 0.5.
  • the GO sheets were added in the amount of 0.05% by weight of cement.
  • the casting procedures for all samples are similar.
  • the cement and liquid water or GO suspension
  • the cement slurries were mixed at 2000 rpm for 5 min using a hand-mixer (Sanyo, SHM500, China).
  • the mixture was then placed into a steel mould which measures 40 mm x 40 mm x 160 mm. Each mould was vibrated for 15 to 30 seconds on a vibration table. All specimens were immediately covered by polyethylene sheets in order to prevent loss of water from the samples.
  • the hardened cement specimen was then demoulded and cured in a calcium hydroxide bath to prevent lime leaching out from the cement pastes.
  • Different curing regimes were adopted for the specimens tested at different ages. For specimens tested at an age of 7 days, they were cured over 7 days. For those tested at the ages of 28 and 56 days, the specimens were cured over 28 days. All the specimens were allowed to dry in the air for 12 hours before they were subjected to mechanical tests.
  • Flexural strength is one measure of the tensile strength of cementitious matrix materials. It is a measure of a beam or slab to resist failure in bending. In the current research, the flexural strength is determined by a 3 -point bending test. This test was carried out using a closed-loop MTS servo-hydraulic testing machine with a 50 kN capacity. The sample was sliced into small beams measuring 15 mm x 15 mm x 80 mm for the bending test. The displacement control rate was 0.1 mm/min so that the maximum load for any specimen was achieved within the first 50 to 90 seconds.
  • the broken half of the specimens was cut into cubes of 15 mm x 15 mm x 15 mm for the compressive strength test.
  • Each face of the specimens was cut using a diamond saw.
  • the surfaces of the specimens were further polished using a grinding machine, which helps to ensure the opposite surfaces are level both perpendicularly and parallel.
  • two linear voltage displacement transducers were used to measure the vertical displacement of the specimen on the left and right sides. During the test, the displacements obtained from two LVDTs were quite close, indicating that the opposite surfaces of the specimen are reasonably parallel.
  • the strain of the specimens was measured by using a laser extensometer of LX 500. This instrument is specifically designed for accurate, non-contact measurement of strain on various materials under tensile or compressive conditions. Resolution of ⁇ ⁇ and elongations up to 127 mm can be achieved. To obtain the post-peak response of specimens under compression, the load was applied at a constant displacement rate of 0.4 mm/min. The high-speed data acquisition systems were used to collect the data including load and strain reading. The stress-strain curves were plotted according to the strain measured by the laser extensometer.
  • Ultrasonic pulse velocity was used to detect internal cracks at millimetre scale.
  • ultrasonic pulse velocities were measured by a commercially available pulse meter with an associated transducer pair.
  • the lightly greased transducers were placed on two sides of the cube specimens (15 mm x 15 mm).
  • the travelling length of the ultrasonic pulse is the distance between opposite surface of specimens, which was measured by using a vernier caliper with a minimum reading of 0.01 mm.
  • mini-slump tests Owing to the very limited amount of cement paste that could be produced, the workability of the produced mixes was assessed by mini-slump tests, as reported by Kantro [13].
  • the dimensions of the mini slump cone mould are: top diameter 19 mm, bottom diameter 38 mm, and height 58 mm.
  • the mould-cone was placed firmly on a plastic sheet and filled with paste.
  • the paste was tamped down with a spatula to ensure compaction.
  • the mould was removed vertically, ensuring no lateral disturbance.
  • the horizontal spread of the paste was measured by a planimeter. Each value presented in Figure 3 is the average of two test results.
  • TEM analytical transmission electron microscope
  • LaB 6 thermionic, lanthanum hexaboride
  • the SEM samples were remanet pieces (5 mm x 5 mm x 3 mm) from cube which had been tested under compression. Fractured surfaces were mounted on the sample stubs and sputter-coated with gold-palladium.
  • Figure 1 (a) displays SEM image of GO sheets from 0.005 mg/ml aqueous GO solution. According to the SEM image, the sizes of GO sheets are widely distributed from less than 1 ⁇ 2 to over 200 um2.
  • Figure 1 (b) shows a TEM image of GO sheets from 2 mg/ml aqueous GO solution. It can be seen that the grid appears to be entirely filled with the GO sheets. This 'visual' effect is due to the enormous surface area of the sheet, thereby providing a large interface between GO sheet and cement matrix. Another striking observation is the rough and wrinkled surface texture of GO sheet, which is commonly observed in the chemically converted graphene sheets (CCC).
  • CCC chemically converted graphene sheets
  • GO sheets are hydrophilic and highly dispersible in water because of the oxygen-containing groups [19].
  • tap water is generally used to make concrete, the GO colloid was mixed with tap water in a ratio of 1 : 1.
  • a visual examination of the GO sheet suspension found that the GO sheets were well dispersed in the tape water solution without any discernable precipitation or suspended particles. This suspension remains stable after at least 1 hr. Workability
  • Pulses are not transmitted through large air voids in the paste and, if such a void lies directly in the pulse path, the waves are deflected around the void and the instrument will indicate the longer time taken by the pulse to circumvent the void. As a result, the time taken for the pulse to arrive at the receiving transducer will be longer than that in a similar paste without air voids.
  • Test results in Table 1 shows that there were no significant differences in pulse transmission time between OPC and GO/cement composite, indicating little entrapment of large air voids even though the GO/cement paste workability was slightly less that OPC. The good homogeneity is further confirmed by the enhanced strength of the GO/cement composite.
  • the weight and dimensions of three beams (15 mm x 15 mm x 80 mm) per mix were measured in order to calculate the density of a particular mix. The calculations were carried out in accordance with the requirements of AS 1012.12.1.
  • the density of individual mixes is presented in Table 1.
  • the density of the GO/cement composite is similar to that of cement paste. This is due to a similar density between GO sheets and cement pastes.
  • composites density is the volume weighed average of the phases 5 (matrix and filler) density.
  • micro cracking first occurs at the nano-scale and the relatively large conventional fibres are far apart in the cement matrix and thus they have less ability to stop the initiation of micro cracks.
  • the nucleation, growth, interaction, and coalescence of micro cracks are the control mechanisms that cause the macroscopic failure of cementitious materials under compression.
  • nanomaterials When nanomaterials are used, they can bridge nano-size cracks due to high aspect ratio (CNTs), or refine the pore structure (Nano- Fe 2 0 3 •and Nano- Si0 2 ) due to void filler effect.
  • nanomaterials may prevent micro cracks from interaction with one another and thereby improving the threshold at which the networks of micro cracks becomes unstable (specimens fails).
  • the result obtained in the current research also demonstrates a relatively high improvement in compressive strength of the composite due to the addition of GO sheets.
  • the stress-strain curves (under compression) for plain cement paste and GO reinforced composite are shown in Figure 4 (a).
  • the elastic modulus taken as the tangent to the stress-strain curve under compression, is summarized in Table 1.
  • the elastic modulus of composites is primarily affected by the stiffness and volume of components. As the weight fraction of GO in the cement paste is only 0.05%, it is of little surprise then that the elastic modulus of the GO/cement composite is close to that of the cement paste.
  • a slight increase in elastic modulus may be due to the decrease in the number of original shrinkage cracks owing to the GO arresting the cracking.
  • the increase in toughness may be caused by the strong interaction between the cracks and the GO sheets, which is attributed to GO's 2D geometry and high aspect ratio. This hypothesis is further supported by an increased tortuosity of crack propagation paths in GO/cement composite as shown in Figure 6.
  • FIG. 5 SEM micrographs showing comparison of crack patterns in the plain cement matrix and GO/cement composite is presented in Figure 5.
  • the plain cement paste ( Figure 5 (a)) showed major cracks usually pass through dense hydration products in a relative straight direction.
  • the GO/cement composite ( Figure 5 (b)) showed a number of fine cracks with occasional branch and considerable discontinuity.
  • the crack deflection process implicit in the tortuous behavior is also observed in GO/polymer composites.
  • GO sheets exhibit unique two-dimensional structure which can effectively deflect, or forced cracks to tilt and twist around the sheet. The process helps to absorb the energy that is responsible for propagating the crack and thereby enhances the toughness of the composite.
  • Makar and Chan [22] observed an acceleration of the hydration reaction when CNTs are added to the cement paste. This is attributed to the fact that CNTs act as nucleating agents for the formation of the C-S-H and/or calcium hydroxide produced in the hydration process. They also found that C-S-H preferentially form on the surface of nanotube bundles as opposed to the surface of the adjacent unhydrated cement grains. As GO sheets and CNTs are nearly identical in their chemical make-up, the preference for nucleation on the surface of GO sheets is also possible. Owing to a much larger surface area and 2D sheet morphology, GO should have a higher surface adsorption capacity when compared to CNTs. Adsorption would trap ions (e.g.
  • the C-S-H phase contains a network of very fine pores called gel pores, giving it an extremely high specific surface area, and making the total surface area of a given cement paste essentially determined by its C-S-H gel content.
  • N 2 adsorption-desorption measurements along with Brunauer-Emmet-Tellet (BET) and Barrett-Joyner-Halenda (BJH) methods of analysis were used. From the adsorption isotherms the specific surface areas were calculated by application of the BET equation.
  • the pore size distribution is presented in Table 3. Analysis of the nitrogen desorption profiles using the BJH model indicates that the addition of GO increases the pore volume of the composites in the pore diameter range of 1 nm - 80 nm. A similar phenomenon is also observed in CNT reinforced cement composite. Results also show a significant increase in the volume of small and medium pores (1 nm - 45 nm) for the composite containing GO sheets. As the pore diameter increases, the difference in pore volume decreases. In the range of 45 nm to 80 nm, the pore volume of OPC and GO/cement is similar. The small pores (1 nm - 10 nm) are primarily gel pores which were composed of pore system in C-S-H gel.
  • a high proportion of gel pore is thus an indication that the addition of GO accelerate the hydration process.
  • the mechanisms influencing hydration due to the presence of GO remain unknown and require considerably more studies.
  • the nucleating hypothesis needs to be further validated by a quantitative analysis of the hydration rate.
  • the hydration process may be also influenced by reactions between the carboxylic acid and the C-S-H or Ca(OH) 2 .
  • Such reactions are believed to be responsible for the formation of strong covalent bonds between cement matrix and GO [15].
  • the general scheme of these reactions can be illustrated in Figure 6. Therefore, the carboxyl acid attached on the basal planes and edges of GO sheets will react with hydration products to form the covalent bonds.
  • a comparison of geometries for GO and CNT show that GO sheets provide larger surface exposed areas to the cement matrix. This feature allows for more potential sites for chemical reactions, resulting in a higher reinforcing efficiency due to the formation of a higher degree of interfacial force between two materials.
  • Kantro DL Influence of water-reducing admixtures on properties of cement paste— a miniature slump test. Cem Concr Aggregates. 1980;2(2):95-102.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
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  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Civil Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

Un aspect de l'invention concerne une composition comprenant un matériau cimentaire, un liquide et une dispersion d'oxyde de graphène sensiblement uniforme sans adjonction séparée de dispersants, de tensio-actifs ou d'agent stabilisants, qui après durcissement forme un matériau matriciel présentant une meilleure résistance à la compression et à la flexion par rapport à un matériau matriciel équivalent sans oxyde de graphène. D'autres aspects de l'invention concernent le matériau matriciel formé à partir de la composition comprenant un matériau cimentaire et des procédés permettant de produire la composition de matériau cimentaire et le matériau matriciel.
PCT/AU2012/001582 2011-12-27 2012-12-21 Ciment et béton renforcés a l'oxyde de graphène WO2013096990A1 (fr)

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