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Similarly, in embodiments where the nano-sized particles include a taggant material, each zone receives proppant carrying tagged nanoparticles where the taggant received in each zone is chemically distinct from that received in the other zone or zones. To analyze the composition of nanoparticles, taggant, or both, a sample containing produced proppant may be obtained. While in the fractures, the nanoparticles fixate formation fines onto proppant particles. The nanoparticles are believed to provide both functions without damage to subterranean formations. That is, dual-function nanoparticles (e.g. produced on proppant) may be chemically analyzed to provide information about their constituents, including the taggant if present. Since nanoparticles and/or taggants can be chemically differentiated, and chemically distinct nanoparticles and/or taggants will be used in different zones, chemical analysis of the nano-sized particles and/or taggants can facilitate identification of the zone from which they originated. Another, different zone may be treated in the same way except the proppant carries another, different type of dual-function nanoparticles and/or taggant material to the other downhole zone. The identity of such nanoparticle(s) and/or taggant(s) on produced proppant may then be used to determine which zone or zones they were produced from, hence where the failure(s) occurred. Thus, the nanoparticles may be used to fix formation fines and the chemical composition of the nanoparticles, the taggant, or both may be used as an identifier. In a simplified, non-limiting example, proppant having one type of dual-function nanoparticles disposed thereon may be suspended in a base fluid and be pumped downhole to the zone being treated. But should one or both of the zones fail for some reason (e.g. produce proppant from the hydraulic fracture), the proppant produced into the well may be analyzed to determine which nanoparticle(s), taggant(s), or both are present on the proppant. Alternatively, and without limitation, produced proppant samples may be obtained by mechanical sampling such as via a downhole wireline with a solids removal tool at the end, or by using a viscosified fluid to sweep out the wellbore. It is expected that samples will usually come from reservoir fluids, such as hydrocarbons, containing solids, such as proppant, that are produced to the surface.
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Generally, to sweep out the wellbore, a viscous pill is pumped from the surface using the existing tubing or a coiled tubing to wash out a wellbore. Magnesium oxide is a suitable material for making dual-function nanoparticles. Chemically, nano-sized particles or nanoparticles may be comprised of metal oxides and/or hydroxides. Embodiments, however, are not limited to metal oxides and/or hydroxides; piezoelectric crystals and pyroelectric crystals are also suitable materials from which nanoparticles may be produced. Magnesium oxide particles and powders are but one example of a suitable alkaline earth metal oxide and/or alkaline earth metal hydroxide particle. Regardless of how the proppant (or other carrier particle) sample is obtained, it may be analyzed by any suitable detection method such as, without limitation, inductively-coupled plasma (ICP), X-ray fluorescence (XRF), x-ray diffraction (XRD), and proton-induced X-ray emission. For example, dual-function nanoparticles may be comprised of materials selected from the group consisting of alkaline earth metal oxides, alkaline earth metal hydroxides, transition metal oxides, transition metal hydroxides, post-transition metal oxides, post-transition metal hydroxides, and mixtures thereof.
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Other suitable alkaline earth metal oxides and/or hydroxides include elements in Group IIA of the previous IUPAC American Group notation, including without limitation, calcium (Ca), strontium (Sr), and barium (Ba). For instance and without limitation, the alkaline earth metal oxides and hydroxides, may be used alone or in combination with one or more transition metal oxide, transition metal hydroxide, post-transition metal oxide, post-transition metal hydroxide, piezoelectric crystal, and pyroelectric crystal. It should be noted that dual-function nanoparticles may be used alone or in combinations or mixtures. In one non-limiting embodiment, specific suitable piezoelectric crystal particles may include, but are not necessarily limited to, ZnO, berlinite (AlPO4), lithium tantalate (LiTaO3), gallium orthophosphate (GaPO4), BaTiO3, SrTiO3, PbZrTiO3, KNbO3, LiNbO3, LiTaO3, BiFeO3, sodium tungstate, Ba2NaNb5O5, Pb2KNb5O15, potassium sodium tartrate, tourmaline, topaz and mixtures thereof. These elements include, but are not necessarily limited to, titanium (Ti), zirconium (Zr), cobalt (Co), nickel (Ni) and/or zinc (Zn). Pyroelectric crystals generate electrical charges when heated and piezoelectric crystals generate electrical charges when squeezed, compressed, or pressed. Dual-function nano-sized particles may also be comprised of piezoelectric crystal particles (which include pyroelectric crystal particles). The total pyroelectric coefficient of ZnO is −9.4 C/m2K. Dual-function nanoparticles may also comprise oxides and/or hydroxides of one or more “post-transition” metals such as without limitation aluminum (Al), gallium (Ga), indium (In), tin (Sn), thallium (TI), lead (Pb), and bismuth (Bi). In one non-limiting explanation, when very small pyroelectric crystals, such as nano-sized ZnO, are added to a base fluid, which is then pumped downhole into underground formations that are under high temperature and/or pressure, the pyroelectric crystals are heated and/or pressed and high surface charges are generated. ZnO and these other crystals are generally not water soluble. These surface charges permit the crystal particles to associate, link, connect or otherwise relate the formation fines together to fixate them together and also to the carrier particles. Non-limiting examples of such suitable oxides include zinc oxide (ZnO), zirconium dioxide (ZrO2), titanium dioxide (TiO2), cobalt (II) oxide (CoO), and/or nickel (II) oxide (NiO). In another non-limiting embodiment, nano-sized particles may be oxides and/or hydroxides of elements of Groups IIB and IIIB of the previous IUPAC American Group notation.
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In some embodiments the dual-function nano-sized particles may be tagged with a taggant material. Of the post-transition metals a taggant may be selected, without limitation, from the group consisting of: Al, Ga, In, Th, germanium (Ge), Sn, Pb, arsenic (As), antimony (Sb), Bi, selenium (Se), tellurium (Te), and mixtures thereof. For nanoparticles of a given composition, the associated taggant should be distinguishable from the nanoparticle primary component. The exact choice of taggant for association with such primary component could also be an oxide phase albeit one with a composition distinguishable from other phases that may be part of the system. Non-limiting examples of suitable transition metal taggants include scandium (Sc), yttrium (Y), Ti, Zr, hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), molybdenum (Mo), tungsten (W), manganese (Mn), rhenium (Re), iron (Fe), ruthenium (Ru), osmium (Os), Co, rhodium (Rh), iridium (Ir), Ni, palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), Zn, cadmium (Cd), and mixtures thereof. It is believed that suitable taggants may be selected from the group consisting of alkaline earth metals, transition metals, post-transition metals, lanthanoids, and mixtures thereof. Of the alkaline earth metals, Sr and Ba are two non-limiting examples of suitable taggants. As a non-limiting example, the primary component of the dual-function nanoparticles may be a mixture of different oxide phases, such as MgO, CaO, SiO2, Al2O3 and the like, the majority of which being MgO.