D3077AL co») United States cz) Patent Application Publication (1 Pub. No.: US 2023/0023077 AI US 202300: ARAMPATZIS (4) Pub. Date: Jan. 26, 2023 (54) SELP-BINDING SUSPENSIONS COMPRISING Bors 2710 (2006.01) TITANIUM DIOXIDE AND ZINC OXIDE, Bors 3500 (2006.01) NANOPARTICLES AND COATED BOLT 37234 (2006.01) SUBSTRATES PREPARED USING ois 3702 (2006.01) BINDING SUSPENSIONS BoId 3708 (2006.01) 2) Use (71) Applicant: NanoPhos SA, Lavrio (GR) cre BOLT 21/063 (2013.01), BOLE 21/066 Goon: Boss 3106 2013.01), BOL 3138 (72) Toventor: Toannis ARAMPATZIS, Lavrio (GR) (01301): BOLI 2771806 2013.01). BOLT S 27/10 (2013.01); BOLT 38/0013 (2013.01), (3) Assignee: NanoPhos SA, Lavrio (GR) Poiana (2013.01); B17 370219 (2013.01), BOTT (21) Appl. Nos TT9H,628 Gols OU} Bee (22) PCT led: Jan, 10, 2020 on ABSTRACT (66) PCT Nos PCHGR2V20/00005 Provide are sel-binding suspensions and cated stbtates § 371 (eX), prepared using seltbinding suspension. Also provided are (2) Date!" ut 8, 2022 Imethods of preparing sel-binding suspensions, Methods - ‘nay inclide preparing © binder solution: preparing a tia ublietien Clastacotin! nium dioxide-vin oxide suspension tsing ultsonication (1) mech ‘mixing the binder solution with the tisinium dioxide-zine Bors 2106 (2006.01) oxide suspension and a surfactant to form a sef-binding Bors 31706 (2006.01), suspension composition; and coating a glass substrate with BOLd 31238 (2006.01) the self-binding suspension composition to form a coated BOS 2718 200601) lass substratePatent Application Publication Jan. 26,2023 Sheet 1 of 6 US 2023/0023077 Al Delonized Water [onic Strength Regulating Salt Dispersant Solution A Titanium Dioxide Raw Powder Zine Oxide Raw Powder 30min String Shanti Diovi 30min String Utresonication ee Utrasonication Suspension Binder Solution Surfactants 20min Stirring ‘20min StringPatent Application Publication Jan. 26, 2023 Sheet 2 of 6 US 2023/0023077 A1 J U FIG. 2 1200. 800+ ity, 2.u. Int 4004 4a hel, deg FIG. 3Patent Application Publication Jan. 26, 2023 Sheet 3 of 6 US 2023/0023077 A1 FIG. 4Patent Application Publication Jan. 26,2023 Sheet 4 of 6 US 2023/0023077 Al 102 Concentration (%) 2eeesen25Patent Application Publication Jan. 26,2023 Sheet Sof 6 US 2023/0023077 Al M4 10 094 084 07 08 05 04 034 02 00 pe 7 a Ef r2n0 ‘80 time(s) FIG. 6 Air polutants concentration (ppm)Patent Application Publication Jan. 26,2023 Sheet 6 of 6 US 2023/0023077 Al So Transmittance 35 525675 825 97h 1125 1275 1425 1575 1725 1875 Wavelength A (nm) FIG. 7US 20230023077 Al LF-BINDING SUSPENSIONS COMPRISING ‘TITANIUM DIOXIDE AND ZINC OXIDE NANOPARTICLES AND COATED SUBSTRATES PREPARED USING 'SELE-BINDING SUSPENSIONS. FIELD OF THE INVE INTION [0001] This disclosure relates to se-binding suspensions for preparing transparent photocatalytic thi films. Specif- cally, this dieleste relates to self-binding suspensions ‘comprising titanium dioxide, zie oxide, and silicon dioxide nanoparticles for enhanced photocatalytic aetvity BACKGROUND OP THE INVENTION [0002] Transparent coatings with ani-fygging, anti-relec- live, photocatalytic and sol-cleaning properties may be used jn products such as windshields, Tenses, oF solar energy devices. Particularly for solar energy devices, the transpar- ‘ent coatings shou! meet certain requirements including ‘enhance the light collection yield; prevent the aging process ‘of the substrate; and minimize maintenance costs. Addition- ally, coatings or thin inorganic films developed for the surface of solar enengy devices should be permanent and have a minimum lifetime of five years. [0003] Conventional nanocomposite formulations and thin flms coatings include TiO, nanoparticles, SiO, nan- ‘particles, andor hydrolyze sikines for hydrophilicity and ‘or improved adhesion. TiO, nanoerysillites exis in three ‘istnet erytal phases: anatase, brookite and rutile. Of these three phases, anatase iz generally preferred for photocata- Iytie activity because of its energy gap inthe range of 3.23 eV (a-type semiconductor). When the photoactive titanium dioxide nanoparticles are iradiated by ultraviolet light (i, Tight having a wavelength below 390m), electrons trom the ‘leciracflled valence hand are transfered to the vacant ‘conduction band and subsequently leave positive-charged holes in the valence band. This photo-generated charge Separation is responsible for potoreduction and photooxi- lation of different target compounds surounding the sem ‘conductor particles. 10004] Conventional methods of improving photocatalytic civily of TiO; include doping. Doping may be achieved ith the addition of dyes, transition metals (eg Cr 2, Mn), nonmetal (@g., N, $, ©), andlor semiconductors (ep, SiO, Sn0,, 220,, 280). Furthermore. doping crystal phases of titanium’ dioxide nanoerystallites can result in better photocatalytic performance and enance photon eap- lure for solar applications, de to the higher reactive index ‘of tile vs. anatase (2,488 for anatase and 2,609 For etie). [BRIEF SUMMARY OF INVENTION 10005] Provided herein are sel-binding suspensions, ‘coated subsrates prepared using selF-binding suspensions, fand methods of preparing self-bnding suspensions. Self binding suspensions provided herein may be prepared using ultmsonication and may bind to a substrate without the pplication of heat. Films produced using the disclosed suspensions may be used (0 produce windshields, lenses, solar enemy devices, and the lke [0006] Sci-binding suspensions provided hercin can be used to prepare high-quality thin films. For example, thin fms used in solar light applications may be transparent in the visible or near-infrared spectrum. If hese thin films are Jan. 26, 2023 ot transparent, they could interne withthe light supplied to the solar eneray converter Further, sch films shot be able to retain thee inital properties (ex. photocatalytic tivity, ntioeflstveaciviy) fr a siniomn of ive years Uuder variable wethce conditions snd exhibit suitable a= Soa to the substrate {0007} Thus. suspensions provided herein incorporate rmonndispersed nanoparticles comprising agglomerates not exceading 200-nm 10 improve the ranspareicy of the hin films produced from the provided svapensions and minimize the satering ofthe visible ight, Further the binary syst of ian dioxide with ine oxide can provide synergistic effets and performance (e, photocatalytic reton rats, ‘overl efietion) that eannot be achieved when either ofthe Siunium dioxide or zine oxide nanoerystallinepartles are present alone In particular the binary system of 0,250 Shows improved photoataltie activiy compared to pure “TO, When the to photoactive oxides (he tanium diok: ide and vine oxide) awe combined, 3 material having Jinproved. photocatalytic activity is generated. This is bots the valence semicondctor bad and the condition semiconductor band postions of each of the independent Tanoparticles are cote to each other sad tend to overlay (030eV for valance band and 2.4 eV for conduction band for tanium dioxkle and 0.32 eV for valance band and 2.88 eV for conduction band for zine oxide). Therefore, the Jnteracton of semicondscors wih close valence condition band positions results in more eflective photocatalytic por formance as) elestron hopping is easier when intermediate bands ar present and) charge separation s more elletve, ie positive oles and negative eleson recombination rte is slaniticanly reduced. {0008} Additional, suspensions disclosed can realy hereto porous or non-porous substrates du to the pes nce of hinder that acts a6 an adhesion promotor (oa, Silicon dioxide) Furber, doping wih in oxide in parc. Jac may be used fr ts high chemical stably high rele tive index, high thermal conductivity, anibacteral proper tis, UV.protastion and somone {0009} In some embodiments, provided is a selbinding suspension composition, the composition comprising Gooo1 to 025 'wt % tani dloxide. nanoparticles; (0.00001 1 08 wt. % zine oxide anopatiles: 107 wi. % sikoxysiane; 0.00025 10 0.00125 wt salt 0.000210 0.01 ‘we be dispersant 0.2 to O8 Wt. 6 suet, 710 12 Wt % cohol; 01 160-2 wi % bie sui: and 801 90 wt. % solvent {0010} 1m some embodiments ofthe composition, the salt comprises at Teast one of Na4P207, sin bydroxie, oF Sodim chloride [W011] Io some embodiments of the composition, the loohol comprise t Test one of methana oF ethanol {0012} “In some embedimen's of the composition, the solvent comprises deionized water. {0013} In some embedimen's of the composition, the Siuaium dioxide nanoparticles are formed fom upping ‘ltsonicaton to tant dioxide powder. {W014} Insome embodiment of the composition, the zine oxide nanoparticles are forme from applying lasonica tion to zine oxide powder (0015) In some embodiments, a coated plas substrate is provided, the costed glass substate comprising: lass Substate: and a tiafiin cating on the lass subst, the thin-film coating comprising: O.ODL 40 5. wt. % titaniumUS 20230023077 Al dioxide powder; 0.0001 w 10 wt. % zine oxide powder: 20, to 35 mt % akonysiane; 0.00025 19.026 wt. 8 sal; 0.002 to 02 w.% dispersant; | to 8 wr." surfactant: 35 to 60 wt % aleahol: and 0.5 to 4 wt. % basic soliton. 10016] In some embodiments of the casted glass substrate, the salt comprises atleast one of Na4P2O7, sodium hydrox. ide, or sodium chloride [0017] In some embodiments of the coated glass substrate, the alcobol comprises at lest onc of methanol or ethanol [0018] In some embodiments of the costod plass substrate, the solvent comprises deionized water. [0019] In some embodiments of the cated glass substrate, 0.01 19 0.03 Lim? ofa selt-binding suspension composition i applied othe las subsite Wo orm the cote st substrate, 10020] In some embodiments of the costed glass substrate, the coated glass substrate comprises a windshield, a leas, oF a solar energy device [0021] In some embodiments, @ method of producing & ‘coated glass substrate is provided, the method comprising preparing binder solution; preparing titanium diowide- ine oxide suspension; mixing the binder solution with the titanium dioxide-ine oxide suspension and a surfactant to form a self-binding suspension composition; and depositing the selP-binding suspension onto a glass substrate to Forma 8 ‘conte lass substrate, 0022] In some embodiments of the method, preparing & binder solution comprises mixing alkoxysilane, an aleohol, a Lewis base, and a first solvent. [0023] In some embodiments of the method, preparing titanium dioxide-rine oxide suspension comprises ultrasoni- fying a salt, a dispersant, titanium dioxide powder, zine ‘oxide powder, and a second solvent. 0024) In some embodiments of the method, the coated lass substrate comprises a windshield, a lens, or a solar energy device. 10025] In some embodiments of the method, the salt ‘comprises at least one of NaP;O,, sodium hydroxide, or sexi ehloride, [0026] In some embodiments of the method, the aleohot ‘comprises atleast one of methanol or ethane 10027] In some embodiments of the meth, the ist Solvent and the second solvent comprise deionized water [0028] "In some embodiments of the method, depositing the sel-binding suspension onto a glass substrate comprises depositing 0.01 to 0.03 Lim? of the sel-binding suspension ‘composition to the glass substrate BRIPP DESCRIPTION OP THE DRAWINGS 10029] The invention will now be described, by way’ of ‘ample oky withreferere the assomperyingdvigs, [0030] FIG. 1 provides a process disgram for preparing Sel-binding suspension, according to some embodiments [0031] FIG. 2 shows the water droplet contact angle oa an Untreated gloss substrate and on a glass substrate teated With a self-binding suspension, according some embod 10032] FIG. 3 shows x-ray difration data from a sample ‘of TiO,—Za0 suspension powder, according 10 some ‘embostiments; 10033] FIG. 4 shows a seaming electron microscope image of @ sample of TiO, —Za0 suspension powder, according to some embodiments; Jan. 26, 2023 [0034] FIG. 5 shows decomposition dats for a sample of | ‘THO,—Zn0 suspension powder and material disclosed in GR20110100056, according to some embodiments; [0035] FIG. 6 shows pas concentrations under ultviolet radiation fora sof-binding suspension, acconding to some fesbodimeats; ad [0036] FIG. 7 shows a transmittance spectrum of glass, ‘aterial disclosed in GR20110100056, and a sample of ‘TiO, 2n0 suspension powder, according o some embod ates, DETAILED DESCRIPTION OF THE INVENTION [0037] Provided herein are self-binding suspensions, ‘coated subsraes prepared using sel-binding substrates, and rcthous of preparing sel-binding suspensions using ull sonication. In particular, the suspensions disclosed herein ‘may’ be used to prepare thin films for products such as windshields, lenses, and solar enemy devices. Due to the binary TiO, -Zn0 system, suspensions provided herein can provide more transparent films with improve photocata- Igtic stivity than suspensions only having one of TiO, or 700. [0038] To achieve these properties, the suspensions pro Vided herein may include nanoparticles that are monadis persed and comprise agglomerates no lager than 200 nm. Self-Binding Suspension Composition [0039] Suspensions provided herein may include at east {wo metal ones, as, a dispersant, @ surfactant, alee, 2 Lewis bat, and a solvent. Hach individ componcat i deseribed in detail bolow. [0040] The meal exides can include Ti 700 nanoparicls. {0041} TiO, nanoparticles may be obtained from a pov: dr. For example a commercially available and low-cost titanium dioxide powder may Be used the titanium dioxide source. Siiuble commercially avilable Gaim dioxide powders can include Evonik Acroxide™ P90, Evenik Aeroxide™ 025, or Kronos KRONOCeu™ 7000 ‘Whe dite in water, colloidal soon is prepare. In some embodiments, sei-binding suspensions provided herein may inciode 0.00001 to Iwi. % 130. powder. In some embodiments, ssi-inding.sespensions provided herein may incioe fess than 1 wt. %, les than O° .%6 Jess han 0.1 wi. Jess than 005 wt, % ess han 001 We 9G, ess than 0.005 we %, less than 01001 wes han les han 0.0001 Wt 6 Tess than (0.00008 ‘st. % THO, powder. In some embodiments, sol-binding Suspensions povided herein may instude more that 0.00001 180%, more dan 0.00005 wt, mre tn 0.0001 wt 6, ‘ore than .0005 9, more tas 001 Wi. %, mre tha (0.005 wt 6 more than 0.01 wt. 9%, move than B05 Wt. %6 6.1 wt.%, oF more than 05 wt. 6 THO, power: Selt-binding sispensios compising inscicntly Iw concentrations of TiO, powder may result in thin fils having too tide pholocstalytic activity. Conversely selbinding suspensions Comprising exceedingly high concentrations of 0; powder ‘may not meet the optical eiteria of coating, transparency [0042] | 250 nanoparicls may be otine fom a powder For example, a commerally available and low-eost zine oie powder may be used asthe zine oxide sores Suitable commercially avilable zine oxide powders may include SiO, andorUS 20230023077 Al BverZine EPM-E™, or Bochemie Nano ZnO. When diluted in water, a colloidal solution an be prepared. Ta. some ‘embodiments, selEbinding suspensions provided hercin may inchide 0.00001 to 1 wl. So Za0 powder. In some ‘embodiments, selE-binding suspensions provided herein may inelnde ess than 1 wt. %, less than 0.5 wt %, less than ‘a1 wi. 8% loss than 0.05 wt. 8%, fess than OT wt. %, less than 0,008 wr. %, Tes than 0.001, %, less than 0.00085 wt. 6 ess than 0.0001 wt. %, or less than 0.00008 wr. % Z0 powder. In some embodiments, self-binding, suspensions provided herein may include more than 0.00001 wt °%, more than 0.00005 wt, %, more than 0.0001 wt. So, more than 10,0005 w. %, more than .001 wi. %, more than 0.005 Ww. 6, more than 0.01 wt. %, more than 0.05 wi. %, 0.1 wt. %, ‘or more than 0.5 wt. % 250 powder. Self-inding suspen: sons comprising insufficiently low concentrations of ZnO powder may not assist the photocatalytic elect. Conversely, elt-binding suspensions comprising excecdingly high con= ‘centrations of Za0 powder may be block incident photons capturing by titanium dioxide nanoparticles and therefore, permanently block the photocatalytic effet. [0043] SiO, nanoparticles may be obtained from a sol-gel procedure, For example, commercially available silicon alkoxide raw materials can be used forthe preparation ofa ‘colloidal suspension comprising SiO. power. Suitable ami hosilanes oF silicon alkoxides can be any compound with chemical formula (H.NC,H;,O\CiH:40:0XC Hames) (Hapa O)Si oF (CHayes ONG Hay ONC HO) (CA; ,0)Sior polyimetiyiiloxane (CH1,O8i), (Coils. 1 Caog OME Hane OSHC He SHC Hoy 8) (Ct,1OXC HO) where Ky Tem, Pe Ys 2 ae positive, integer numbers from Zero to eight and g is Positive integer numbers from zero to one thousand). Por ‘example, commercially available akoxysilanes can include DOWSIL® 7.6162, DOWSIL™ Xiameter 6697, andior Dynagylan A. In some embodiments, the colloidal SiO, nanoparticles prepared from a sol-gel technique may be preferred (© SiO, nnoparicles obtained from powders cause they can enhance the superhydeophilicity of the final coating and aet as adhesion binders tothe substrate 1004] In some embodiments, self-binding, suspensions provided herein may comprises 1 to 15 wt. % alkoxysilane In some embodiments, sel-binding suspensions provided herein may comprise les han TS wt. 86, Tess than 12 wt 6, less than 10 wi. %, less than 8 wt. %, less than 6 w1.%, less than 4 wt. %, of less than 2 wr. % alkoxysilane. In some ‘embodiments, self-binding suspensions provided herein may comprise more than I wt %, more than 2 Wt %, more than 4 wt. %, moge than 6 wi. %, more than & wt. 9% more than 10, %, oF more than 12 wt, % alkonysiane 10045] In some embodiments, self-binding, suspensions Provided herein may include a salt. For example, a salt may be used to contol the ionic strength of the preparation ‘emulsion or suspension, Salts dissociate in aqneons media to ions (ionic strength increase). Ions are absorbed on nanopar- ticle surface and electrostatcaly repel each other to prevent ‘agglomeration and sedimentation, Therefor, fine tuning of jonie strength results in more stable nanoparticle emulsions tnd. increase their commercial exploitation potential. To ‘control the ione strength of the preparation solution, the salt, may induce electrostatic interactions between the ionic ‘double layers surrounding the TIO. and ZnO nanoparticles. Examples of suitable silts include polyelectrolytes (ea poly(sodium styrene sulfonate), Na,P.O., sodium hydox- Jan. 26, 2023 ie, o sodium chloride. In some embodiments, salf-binding Suspension provided herein may incude 0.06001 0.005 wwe 9% sult In some embodiments, tbe amounts, 2 sel Binding suspension may inode less than 0.008 wt, ess than 0.0023 6 less than 0.00 wt. %, les han 0.0005 {WE %, less than 0001 Wt 4, oF les thi 0.00008 Wt. 96 Salt. In some embodiments a Seltbinding suspension may fnelude more than 0.00001 wt more than 80005 tore than 00001 we. %, more dun 0.0005 wt 9% oF mors than 0001 6 salt Selthinding suspensions incinding an insuiciuy low amount of salt ay present sedimentation ‘within our afer preparation, making the resulting forme lation impractical to ise. Conversely, selE-binding suspen sions inelatng exeeedingly high concentrations of salt may result in raiced photoatalytie activi, a salt fons erste multilayer around nanoparticles and prevent chenical intr ‘tin With water or oxygen molecules. {0046} Self-binding. suspensions provid hersin may Include a dispersant for promoting the fomation and stabi- Taaon of te nanoparticles inthe soluten. For example, commercially available dinperans can inhale Surya CEBI, Tego Flow 425, carboxylmetyl cellulose (CC), Eat slfoxide (DMSO), 1 2-Dipalmitoslsn-alyeeo-3 phosphosholine, Tween 80, bovine serum albumin (BSA), {ud fetal bovine seu (TBS) In some embodiments sel binding suspensions provided herein my iaclude 0.0001 to O11 wt % cispesant. In some embodiments, self-binding suspensions may include fess han 0.1 wt fess than 003 ‘we fess than 0.01 wa 6 fess han 0.008 wa 6 fess han Door wt % or less than 0.0005 wt. % dispersant. In some embodiments, slf-binding suspensions my inclnde more {han 0.0007 wi more hn 0.0008 wt. %, moe than 0.001 181%, more than 0.008 wt. %, more than OO1 Wt %, oF tore thin 005 wi. % dispena (0047) Selfbnding. suspensions provided herein may Jnelude a surfactant. Surfactants may elp improve substrate Weting by reducing the surfice tension betwecs the sel Binding sumpensionthin fil and the sibetrate, Suitable commercially available surfactants may ince Tepo Wet $00, Tego Wet 270, and siloxane Formulations. i some embodiments, selfbinding suspensions provided erein tay include 0. 5 wt. % strfctant In some embodie ‘ents, sel-binding suspensions may iclide less than $ Wt 3%, tess than 4 w%, fess than 3 wi. Mo Hess than 2.6 Jets than 1%, oF es than 0.5 Wt 9 surfactant In some embodiments, selt-inding suppeasion: may include more than O.1 wt 8, more than 0.5 Wt %, more than T Wt. 56 snore than 2 wt more than 3 wt, 8, oF ore a 4 Wwe % sarfactant. [0048] In some embodimens, selbining suspensions provided herein may inchide a lguid sleobol wo hydrolyze the chemical Binder. A stale alcohol my inchade op to five eatbon atoms (eg. methaool, ethanol and up wo two oxygen atoms (Cly,;0 oF Glg.Os, where i ind j are pole integer numbers om ne five, nse embodi- ‘ments, selbinding suspensions provided! her may include 1Tto 25 wi, % aleobo. In some emia, sl: bind suspensions may inci ess than 28 wt, les than 20 We yess than 15 Wt %, less than 10 st %,or less than $ Wt ale in some embodiments, suspensions may include more than 1 wt % more than 3 wi 6, mote than 10-6. %6 more than 15 wt, %, o@ more that 20" wt. % aloo [0049] In some embodiments, a Lewis base may be Included ina supension provided herein to adjust the pHUS 20230023077 Al ‘ale dring hydrolysis In some enbeiments, the pH may he adjusted and controled toa value from 9 © 10- In some ‘embodiments, selbinding suspensions provided hercin say inclnde 001 10 0.5 wi. % Lewis bse. In some embod tient, selFbinding sispeasons may inelude Tes Hn 0 ‘we 6: es than Owe es than 0.3 wi es than 0.2 Wt %, Less than 0.1 wi. %, or ess than 0.08 wt % Lewis hase. In some embodiments, sef-binding suspensions may include more than QOL wt. 8, more tha 0.05 Wt oe are than O1 wt. %, more than 02 Wt, more than 0:3 wT. ‘or more than 0.4 wt % Lewis base, 10050] Sebinding suspensions provided herein. may include solvent Stable solvents can inlade water (©, {onizal) oF akobol. In some embodiments, sele-binding suspensions providd herein may’inciwle 75 to 95 wt % solvent In some enbodimens, selPbinding suspensions tay inde tes than 98 fess than SO wt fess han 85 Ww. %, or les han 80 wt. % solvent ln some embod nent, seiPbinding suspeasions may ited more than 75 ww, more than 80 wr. more than 85 wt. %, or more than 50 wt. 8 solvent Costed Substrates [0051] The above-described selPhinding suspension can be use to prepare costed substrates for applications inti ing, but not limited to, windshields, lentes, andlor solar ‘energy devices. Discussed below are various application! ‘deposition methods for prepating costed substrates [0052] Sci-binding suspensions provided can he consid- ‘ered “SelP-binding” due to the ability of particularly the nanoparticles in the sef-binding suspension to easily adhere to the substrate. Specifically, the silicon oxide nanoparticles sot a binder. In Some embodiments, no heat treatment step is necded for the self-binding suspension to adler to the substrate, 10053] In some embodiments, « self-binding suspension may’be used to form the coating on a tin-ilm substrate. For ‘example, 0.001 to 0.1 Lim? of sel-binding suspension may’ be deposited to the substrate, In some embodiments, less than 0.1 Lim, loss than 0.08 Lin, less than 0.06 Lim loss than 0,04 Las, les tha 0.02 Lim, less than 0.01 Lin’, oF less than 0.005 Lim sel?-binding suspension may be depos- ited on a substrate. In some embodiments, more than 0.001, Lim? more thn 0.005 Lim? more than 001 Lim’, more than 0,02 Ls, more than 0.04 Li, more than 0.06 Lin", ‘oF more than 0.08 Lim? selfbinding suspension may be ‘deposited on a substrate 10054] In some embadiments, the substrate of the coated Substrate may comprise an organic or an inonganic material For example, suitable substrate materials may include glass, ‘slumiaum, metal substrates, cement and concrete, plasters ‘and renders, polymer flms, polycarbonate films, serie Paint fms, styrene-seryli point films, polyurethane paint fms and epoxy paint films, Example 1 10055] FIG. 1 shows the flow chast of a preparation process of a selF-binding suspension, aeconding to some ‘embodiments. As shown in the figure and explained in detail, below, the binder solution is prepared separate from the Ti0,/2n0 colloidal suspension and combined in the final step to form a selF-binding suspension according to embodl- ments provided herein Jan. 26, 2023 [0056] Preparing the Binder Solution: Twenty Liters of alkoxysilane (1,6-bis(trimethoxysilyhexane; DOWSIL™ Z-6162, Dow Coming Europe SA) were mixed with 1 L of ‘icthanol in stainless ste! 200 [chemical reactor. Deion- ined water (75 L) was added to the mixture and sted for five minutes. A water-soluble Lewis base (25 wt. % ammo: nium hydroxide NH,OH) was added droprvise w adjust the plT to 95. The mixture was stired for 600 minutes until becoming a transparent liquid. [0057] Preparation ofthe Ti03/Za0 colloidal suspension: Deionized water (150 L) was placed into a 250 L stainless steel coatinuously string tank reactor. stabilizing salt (Na,P.0,, 0. kg) and 0.075 kg of dispersint (Surijnol (C1331, Air Products and Chemicals, Inc.) were diluted into the deionized water. The solution was vigorously stired for 6 minutes at 600 rpm. After string. 0.75 ky dtanium dioxide powder (Evonie Acronce™ PO) and 0.075 kg zinc oxide (EverZine EPI) were added to the solution, resulting in a colloidal solution [00S8] A Heilscher, UIPIOOONd ultrasonic processor (poser ousput: 800° Watts at 20° KHz) having a robust stainless stool reactor vessel was connected t the contin ous-stiring tank reactor for 30 minutes, The ultrasonication ‘ip was connected inthe colloidal solution. fier 30 minutes of ultrasonication, the resulting material was a stable TiO, 700 suspension. {0059} Preparation of Final Sel-Binding Suspension: As \epieted in FIG. 1, the binder solution and the Ti0,—Za0 suspension, the preparation of each of which is described above, are combined with the surfactant (EVONIK, Tego ‘Wer 500), The combination is mixed and stireed for 20 snutes at 600 gpm. The product is stable for at least six ‘months (ie, litle or no sedimentation oF precipitation of solid phase). Additionally, the resulting suspeasion may be Applic to substrates using industrial deposition methods [0060] Table 1 below, provides the weight-pereent of each of the components described with respect to Example I “0,200 supa Ho sansa Replat bins ia Sate Ricg Super Binks Sion 50 nema *3 10,00 “as Example 2 [0061] FG. 1 equally applies to the process of Example 2, Aeseribed below, ait does with Example IAs shown in theUS 20230023077 Al figure and explained in detail below, the binder solution is prepared separate from the TIO,/Zn0 colloidal suspension ‘and combined in the final step to form a suspension accord ing to embodiments provided hercn, 10062] Preparation of the Binder Solution: Twenty Liters of alkoxysilane (teruethoxy silane; DOWSIL™ Xiameter (6697, Dow Corning Europe SA. andlor EVONIK™, Dyna- sylan A) were mixed with IL of ethanol in a 200Lsainless Steel chemical reactor, Deionized water (7 L.) was added to the mixture and stimed for 3 minutes. Sodium hydroxide in ‘an agheous solution was added dropwise to adjust the pH 10 5.8. The mixture was sted for 600 minutes ual ta parent liquid was achieved. [0063] Preparation ofthe TiO./2n0 colloidal suypenso Deionized water (1301) was placed ina 250 stainless ste! ‘continuous stirring tank reactor. The stabilizing salt (0.25 ke, NaCl) and 0.07kg of dispersant (Surfyno! CT-23i, Air Products and Chemicals, Ie.) were diluted in the deionized ‘water. The solution was vigorously tiered for 60 minates a 600 rpm. Aer string, 0.65 kg of titanium dioxide powder (Evonik Aeroxide™™ P90) and 0.013 kg of zine oxide (Ever- Zine EPM-E™) are added to create a colloidal solution. 10064] Hielscher, UIPIOOid ultasonic processor {power output: 800. Watts at 20 KHz) having a robust Sainless stool reactor vessel was connected to the continu ‘ous-stirring tank reactor for 30 minutes. The ultrasonication tip was consocted in the colloidal solution, After 30 minutes ‘of ulksonication, the resulting material was stable TiO2—Zn0 suspension. 10065] Preparation of the Pinal SelE-binding Suspension AAs depicted in FIG. 1, the binder solution and the TiO; ZO suspension, the’ preparation of each of which is described above, afe. combined with the surfactant (EVONIK, Tego Wet 270), The combination is mixed and Stir for 20 minutes at 600 rpm. The product is stable for at least six months (ie, litle or no sedimentation or pre= ‘ipitation of solid phase). Additonaly, the resulting suspen- sion may be applied to substrates using industrial deposition methods 10066] Table 1, provided above, provides the weight- pervent of each’ component described with respect 10 Example 2 Example 3 10067] Applying the Prepared Suspension to Glass Sub- strates: The prepared solf-bnding suspension (ie, the sus- pension of Example I or Example 2) was mist ai-prayed ‘onto glass subsirates. Specifically, the amount of suspension that was deposited onto the glass substrate was 0.0285 Lia The wet suspension dried and resulted in an immobilized Si0,/110,/200 thin film, Note that no heat treatment was used, [0068] FIG. 2 shows the contact angle of a water droplet fon an untested glass substmte and on a glass substrate ‘coated with a thin film formed from a suspension according to embodiments provided herein. The contact angle was measured using # computer-contolled optical ensiometer Results show that contact angle of water with the coating is Tess than 10 degrees, therefore intense hydrophilicity is ‘observed. As shown in FIG. 4, the high cantct angle ofthe Water droplet on te treated glass substrate demonstrates that the thin-flm coating prepared using suspensions according. to embodiments provided herein are hydrophilic. Jan. 26, 2023 {0069} FIG. 3 shows x-ray difration data oblsined from ‘TiO, 200 suspension powder. In particular, FIG. 3 shows the XRD characteristic peaks obtained from the TiO.JZa0 colloidal sspension. The marked peaks (marked with nom- bers) ae in accordance withthe characteristic peaks of pure ‘TIO, nanoparticles, In detail, the observed peaks for THO, ate: 24.20" (A), 27.30" (R), 37.79" (A), 48.01° (A), 53.79" (A), 62.73° (A), 68.79° (A), 70.00" (A) and 75.10° (A), which correspond to the (101), (110), (004), (200), (105), (204), (116), (220), (116), (220) and (215) erystal planes for pure TiO,, The symbols A and R denote antase snd rutile phase, respectively. Prom the XRD-pattem it is lear thatthe TO, nanoparticles consist from «wo crystal phases; ane is ‘asatase andthe other is rile. In addition, i= posible to calculate the ratio of anataseiraie in te solution from the relative intensities. By using the equations A(%)-100/{1+ 1265(Iy1)} and R(%6)-100-A%), the mass ratio of nataserutle in our solutions is 80%6/30%. Where A(%) and R@6) ae te percentages of anatase and rutile, respectively Ip is the intensity comresponds to the main peak for ratile (110) at angle 26 equal to 27.30" and 1, is the intensity corresponds to the main peak for anatase (101) at angle 20 fegal to 24.20° . This mass percentage 80120 is in totally jcordance with the specilicarions provided for the raw naterial used for preparation ofthe samples. Inthe ease of 200 nanoparticles the peaks are allocated at angles 20 ‘around 32°, 34°, 36°, 47", 57°, 63°, 66°, 68” and. 69° tormespond to the (108), (002), (101), (102), (110), (103), (200), (112) and 201) erystal planes for pure Zn0 nanopae tiles should be notied that the peaks of Z1n0 due to the low percentage used in the solutions canbe sifted depend- ing the composition of the solution, For the 70 nanopae ticles the main peak i at 36.38° which corresponds to (101) ceystal plane. For this reason the quantitative analysis for calculation ofthe ZnO percentage iseilicut in the presence ‘of HO, nanoparticles, in addition, the XRD peaks are very shacp indicating thatthe NANOPARTICLE are crystalline ‘nd well within the nano-range, Owing to this fet, by using the Scherrer equation d-0,5h/1 eos 8, (where dis the mean size ofthe nanoparicles, isthe X-ray wavelength equal to 1.542 A, Bis the peak width at half the maximum intensity tnd 6 ie the angle comesponding to the main peak), we calculated that the nanoparticles which form the 110,20 suspension isin in the range of 26 1m. [0070] FIG. 4 shows a scanning electron microscope mage obtsined from TiO,—Z0 suspension powder. As shown in the figure, the powder comprises nanoparticles and porosity, which ean extend the surlace area of the powders From the seaaning eleeiton microscope characterization itis obvious that the primary nanoparticles do not exceed the size of $0 nm. [0071] Evaluating the Photocatalytic Activity of the Self [Binding Suspension: The photocatalytic activity ofthe fal seltbinding suspension was evaluated by two procedures (1) degradation of methyl orange (pollutant, organic com pound) under UV illumination: and (2) by siele oxide (inorganic pollutant) oxidation ander UV and visible ight ieraiaton, [0072] The fist procedure, deyradation of methyl orange, ‘was conducted using round:-bottom photocatalytic eels with f near UV-trnspareat window (ext off low 340 nm). A laboratory.consitucted iradition box equipped with four Sylvania GTE [SW FISW/TS blacklight blue Muorescent Tight tubes was used. The photon source had « maximumUS 20230023077 Al ‘emission at 350-nny and emitted 71.7 jWem to simulate hatural sunlight. The concentration was corelated to the ‘absorption ofthe methyl orange solution at 464 am, using 3 single beam Shimadns UV 1240 spectrophotometer. The sample was stirred chroughout the procedure [0073] Based on the methyl orange degradation test the final self-binding suspension demonstrates improved pho~ tocatalytc properties compared to the colloidal suspension ‘of GR20110100056. FIG. § shows the decomposition of methyl orange as a function of time for the material of ‘GR20110100056, and the selP-binding suspension of the present invention. In particular, FIG. 5 shows the degrad~ tion of methyl orange versus time for each of these 10 samples. [0074] ‘The second procedure nitric oxide oxidation under UC and visible light irradiation, wos evaluated under UV-A Tight ilumination with intensity 10 Wim. The duration of the experiments was almost 5 b, The NO gas was supplied from gat container with $0 ppm NO concentration in nitrogen Na. The NO concentration in the reactor was ‘adjusted to 1 ppan aad the relative humidity was kept at 50% using dy and wet air The NO gas flow rate over the samples was approximately 3 Limi, Vader UV illumination, NO pas was adsorbed on the surface of photocatalyst and succes- sively oxidized fo NO, ga fist and then to nonvolstile nites, The NOx concentration in the ie was retrieved by the summation of NO and NO, concentrations. The mea semen rests are presented in FIG. 6. The photocatalytic study includes measurements of the NO monoxide, mea surements of the NO, dioxide and determination of NO, Femoval. The investigated sample with photocatalytic mate= rial exhibited stable photocatalytic activity in NO, removal ducing $b illumination period and revealed production of NOs gas inthe range of 20% [0075] FIG. 6 shows gas concentration under ultraviolet inradiation of a sell-binding suspension. As shown in the Figure, nitric aeid oxidation shows superior photocatalytic behavior under visible light irmdistion. This behavior is ‘easily atibuted to the favorable modified band gaps edges ‘existing in the presented temary system, 10076] FIG. 7 shows atransmittance spectrum of unteated lass, glass treated with material of GR20110100086, and Blass tested with the sell-binding suspension described herein, As shown in the figure, the glass teated with the sel-binding suspension described herein consistently trans- mits more light than untreated glass orth gla treated with material of GR2O110100056, across wavelengths 3 197Sam. 10077] "Aging Test: The adhesion behavior of coatings Prepared using sel-binding suspensions provided herein ‘vas tested using an aging test. In particule, the aging test ‘geconing a ISO EN 11507 was conducted, During the test, hho coating exfoliation wae observed (Le, m0. physical ‘change on the surface ofthe coated glass). [0078] The preceding description sets forth exemplary methods, parameters and te lke. It should be recognized, however that such description snot intended as. imitation ‘on the scope othe present disclosure but ix instead provides asa description of exemplary embodiments. The illustrative ‘embosliments described above are not meant 10 be exhaus= tive orto limit the disclosure tothe procise forms disclosed Many’ modifications and variations are possible in view of the above teachings, The embodiments were chosen and described to best explain the principles of the disclosed Jan. 26, 2023 techniques and their practical applications, Others skilled in the ant are thereby enabled to best ulize the techniques, and various embodiments with various modifications as are sited tothe particular ose contemplate. [0079] Aldough the disclosure and examples have been thoroughly deseribed with reference to the accompanying figures, i is 10 be noted that various changes ane! mod cations will become apparent to those skilled inthe at Such changes and modifications are to be understood as being ‘included within the scape of the disclosure and examples 2s efined by the claims. In the preceding description of the fisclosure and embodiments, reference is made to the accompanying drawings, in which are shown, by way of iMlustaton, specific embodiments that can be practiced. Icis to be understood that other embodiments and examples can be practiced, and changes can be made without departing trom the scope ofthe present disclosure {0080} " Although the preceding description uses tems frst, second, ete, 10 describe Various elements, these elements should not be limited by the tems. These teams are only ‘sed to distinguish one element from another [oo81]. Also, ii also to be understood thatthe singular orms “2,” “an,” and “the” used in the proveding description fare intended 10 include the plural forms as sell unless the ontext indicates otherwise, It salto to be understood that the term “andlor” as used herein refers to and encompasses ‘any and all possible combinations of one or more of the ‘associated listed items, Is further to be understood that the terms “inches, “including,” “comprise.” andor “compris ing.” when used herein, specify the presence of stated ‘ealures integers, steps, operations, elements, components, andlor units at da noe prelude the presence or addition of one or more other features, integers, steps, operations, tlements, components, units, andlor groups thereat. [0082] ‘The tem “if” may be construed to mean “when” or “upon” o “in response to determining” or “in response 10 detecting,” depeading on the context [0083] “Although the disclosure and examples have been Tally deserited with reference to the accompanying figures, its to be noted that various changes and modifications will become apparent to those skilled in the at, Such ehanges ‘and modieations are to be understood as being included ‘within the scope of the disclosure and examples as defined by the claims 1. Aself-binding suspension composition comprising: 0.0001 10 0.25 wt. % titanium dioxide nanoparticles 0.00001 to 05 wt % zine oxide nanoparticles: 4 10 7 wt. % alkonysilane, (0.000025 to'0.00125 wt % salt (0.0002 1 0.01 wt. % dispersant; 0.2 10 0.8 wt. % surfscta To 12 w1. % aleohol, 0.1 1902 wt. % basic solution; and 80 t0 90 wt % solvent 2. The composition of claim 1, wherein the slt comprises at least one of Na,P;O,, sodium hydroxide, oF sodium chloride, 3. The composition of claim 1, wherein the alcohol comprises atleast one of methanol or ethanol 4. The composition of claim 1, wherein the solvent comprises deionized water 5. The composition of claim 1, wherein the stanium Jioxide nanoparticles are formed fom applying ultason tation to titanium dioxide powderUS 20230023077 Al 6. The composition of claim 1, wherein the zine oxide nanoparticles are formed from applying ultrasonication 10 zine oxide powder "7. A conted glass substrate comprising: a pls substrate; and 1 thin-film coating on the glass substrate, the thin-im coating comprising: 0.001 to $ wt. % titanium dioxide powder (0.0001 to 10 wi. % zine oxide powder, 20 10 35 wt % alkoxysilanc: (0.00025 v0 0026 wr, % salt (0.002 40 0.2 wi. % dispersant, 110 8 wt. % surfactant, 3810 60 wt % aleobol: and 05 to 4 wt. % basic solution, 8, The coated glass substrate of elaim 7, wherein the salt ‘comprises at Jest one of Na,P,O,, sodium hydroxide, or soditm chloride 9, The coated glass substrate of claim 7, wherein the sleohol comprises atleast one of methanol or ethanol 10. The coated glass substrate of claim 7, whorein the solvent comprises deionized water. 1 The coated glass substrate of claim 7, wherein 0.01 to 0.03 Lim? of self-binding suspension composition is applied to the glass substrate to form the coated glass substrate, 12. The coated glass substrate of elsim 7, wherein the ‘coated glass subsrate comprises « windshield, a lens, ora solar energy device 13. A method of producing a coated glass substrate ‘comprising: Jan. 26, 2023 preparing a binder solution; preparing a titanium dioxide-rine oxide suspension; xing the binder solution with the tanium dioxide-zine coxide suspension and a surfactant to form a self binding suspension composition; and ‘Sepositing the self-binding suspension onto glass sub- Site to form a coated glass substrate 14. The method of claim 13, wherein preparing a binder solution comprises mixing alkoxysilane, an alcohol, a Lewis base, and first solvent. 15, The method of claim 13, wherein preparing titanium Jioxide-7ine oxide suspension comprises ‘ultrasonifying. a silt a dispersant, Ganium dioxide powder, inc oxide powder, and a secon solvent 16, The method of any of claim 13, wherein the coated lass substrate comprises a windshield, a Tens, ora solar feneray devies. 17. The method of elim 18, wherein the slt comprises at least one of Na,P,0;, sodium hydroxide, or sodium ehlo- Fide 18, The method of elsim 14, whersin the aleahol com pris at least one of methanol or ethanol 19. The method of claim 14, wherein the first solvent an the second solvent comprise deionized wate, 20, The method of elsim 13, wherein depositing the self-binding suspension onto a glass substrate comprises ‘depositing 0.01 40 008 Lim of the sef-binding suspension composition tothe glass substrate