Patent Application: US-201615265573-A

Abstract:
carbon nanotube immobilized membranes for harvesting pure water from air include cnts incorporated into a layer of super - absorbing polymer . the super - absorbing polymer may be cast over a porous substrate . the super - absorbing polymer binds strongly to water and generates water clusters while the cnts are operable to interrupt the specific water - polymer and water - water interactions to generate more free water which permeates more easily through the membrane . methods of forming the cnt immobilized membranes are provided . the cnt immobilized membranes disclosed herein exhibit improved water vapor extraction efficiency , water vapor removal and mass transfer coefficient .

Description:
the present invention now will be described more fully hereinafter with reference to the accompanying drawings , in which illustrative embodiments of the invention are shown . in the drawings , the relative sizes of regions or features may be exaggerated for clarity . this invention may , however , be embodied in many different forms and should not be construed as limited to the embodiments set forth herein ; rather , these embodiments are provided so that this disclosure will be thorough and complete , and will fully convey the scope of the invention to those skilled in the art . well - known functions or constructions may not be described in detail for brevity and / or clarity . the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention . as used herein , the singular forms “ a ”, “ an ” and “ the ” are intended to include the plural forms as well , unless the context clearly indicates otherwise . unless otherwise defined , all terms ( including technical and scientific terms ) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs . it will be further understood that terms , such as those defined in commonly used dictionaries , should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein . now referring to fig1 , a polymeric membrane 2 includes a layer 10 including carbon nanotubes ( cnts ) immobilized in a super - absorbent polymer ( sap ). for the sake of brevity the layer 10 including cnts immobilized in the sap may be referred to herein as the cnim - sap layer 10 . the cnim - sap layer may be further disposed on a porous substrate 20 . the carbon nanotubes may be any suitable carbon nanotube such as those commercially available from cheap tubes inc ., brattleboro , vt . the cnts may be single or multi - walled . the diameter of the cnts may range from about 1 nm to about 100 nm . the length of the cnts may range from about 1 to about 25 μm . in some embodiments the cnts are carboxylated . in general , super - absorbent polymers ( saps ) are materials that have the ability to absorb and retain large volumes of water and aqueous solutions . as is known to those skilled in the art , the absorbing capacity of a sap depends at least in part on the ion content of the water or aqueous solution being absorbed . as used herein , in some embodiments a super - absorbent polymer ( sap ) is any polymer that can absorb and retain at least 100 times its weight in deionized and / or distilled water . in accordance with further embodiments , a sap may be any polymer that can absorb at least 27 times its weight in 1 % saline solution . suitable saps include but are not limited to cross - linked poly ( acrylamide - co - acrylic acid ) and salts thereof , cross - linked sodium polyacrylate , etc . in some embodiments the sap is poly ( acrylamide - co - acrylic acid ) commercially available from sigma - aldrich ( st . louis , mo .). the porous substrate 20 may be formed of any suitable material , such as but not limited to polymers or mixtures thereof , heterogeneous solids , metal , ceramic , etc . exemplary suitable polymers include but are not limited to cellulose acetate , cellulose esters ( ca , cn , and ce ), polysulfone ( ps ), polyether sulfone ( pes ), polyacrylonitrile ( pan ), polyamide , polyimide , polyethylene ( pe ), polypropylene ( pp ), polytetrafluoroethylene ( ptfe ), polyvinylidene fluoride ( pvdf ), polyvinylchloride ( pvc ). the porous substrate may be formed in various configurations such as a sheet , film , etc . in some embodiments the porous substrate is a polypropylene hollow fiber material such as but not limited to celgard x - 20 polypropylene . in one embodiment the cnim - sap layer 10 is made by functionalizing the cnts to a carboxylated form using techniques known to those skilled in the art . cnts are dispersed in water such as by sonication . the sap is dissolved separately in water to form a copolymer solution . the sap copolymer solution is added to the cnt dispersion to form a sap - cnt mixture . the sap - cnt mixture is then applied to a substrate 20 and dried , forming a cnim - sap layer 10 . in some embodiments the substrate 20 may be pre - treated to provide enhanced adhesion between the porous substrate 20 and the cnim - sap layer 10 . for example , in cases in which the porous substrate 20 material is hydrophobic , such as is the case with polypropylene , the porous substrate 20 may be hydrophilized , such as by treatment with chromic acid , and then after hydrophilization , the sap - cnt applied to achieve a composite membrane structure as shown in fig1 . poly ( acrylamide - co - acrylic acid ), potassium dichromate ( k 2 cr 2 o 7 ), sulphuric acid ( 95 . 7 % purity , acs reagent ), and acetone ( 99 % purity ) were obtained from sigma - aldrich ( st . louis , mo .). n2 high purity ( air gas , nj ) and deionized water were used in the experiments and examples . raw multi - walled carbon nanotubes ( cnts ) were purchased from cheap tubes inc ., brattleboro , vt . the average diameters of the cnts were about 30 nm and a length of up to 15 μm . celgard x - 20 pp hollow fibers were employed as a porous substrate 20 . the raw cnts were functionalized to their carboxylated form in a microwave accelerated reaction system ( mode : cem mars ) using methods published previously . see , chen , y et al ., microwave - induced controlled purification of single - walled carbon nanotubes without sidewall functionalization , adv . funct . mater . 2007 , 17 , 3946 - 3951 . the cnts were treated with a mixture of concentrated sulfuric acid and nitric acid solution at 140 ° c . for 20 min in the microwave to form carboxylated cnt analogs . these were washed , filtered and dried under vacuum at 80 ° c . the cnts were carboxylated to be more hydrophilic so that they could interact with the water vapor and be compatible with the sap phase . a hollow fiber membrane module was prepared within a 30 cm long stainless steel casement with male tee connectors placed at each end of the module . the casement and hollow fiber strands were sealed using a fast drying epoxy resin ( resin technology group , llc , s easton , mass .). the sealed “ t ” units prevented intermixing of the lumen and permeated contents and served as the inlet / outlet for the sample and the permeate . the effective surface area of the module was calculated as 94 . 03 cm 2 . 0 . 1 wt % carboxylated cnts were dispersed in water via sonication for 3 hrs . the — cooh functional groups provided good dispersibility . the poly ( acrylamide - co - acrylic acid ) sap was dissolved separately in water under stirring condition overnight to form a copolymer solution . this copolymer solution was then added to the cnt dispersion and the mixture was mechanically stirred for 3 hrs . celgard x - 20 pp hollow fibers are highly hydrophobic in nature , and therefore they were hydrophilized by chromic acid treatment to make a compatible surface and for better adhesion with the sap film . after hydrophilization , the aqueous solution of sap - cnt was passed through the bore of hydrophilized membrane hollow fibers at a low flow rate . the excess solution was removed by flushing the air at very low flow rate through the module . the module was then placed in an oven at 60 ° c . for overnight for further annealing . the composite membrane structure was as depicted in fig1 . the cnim - sap membrane was characterized by using scanning electron microscopy ( sem , leo 1530 vp , carl zeiss smt ag company , oberkochen , germany ). this was done by cutting the membranes into 0 . 5 cm long pieces and coating with carbon films . thermogravimetric analysis ( tga ) was used to investigate the degradation of modified membrane materials during heating . tga was carried out using a perkin - elmer pyris 7 tga system at a heating rate of 10 ° c ./ min under air . the glass transition temperature ( tg ) was measured using a differential scanning calorimetry ( dsc ) analyzer ( model dsc822e , mettler toledo , switzerland ). the temperature range for these experiments was 0 - 250 ° c . at a scanning rate of 10 ° c ./ min . contact angle measurements were made to study the hydrophilic nature of the cnim - sap . these measurements were performed using a digital video camera mounted at the top of the stage . the sorption isotherms were measured as follows . flat cnim - sap membrane was prepared from its aqueous solution by casting over a teflon sheet . the dried and pre - weighed membrane was placed in a temperature control box . water vapor at different concentrations was generated from a water sample and circulated with constant low flow nitrogen to maintain a particular rh in the system . the weight of the membrane was measured at different time intervals till saturation . sorption experiments were also conducted at three different temperatures , i . e ., 30 , 40 , and 50 ° c . now referring to fig2 , an experimental setup for water vapor removal from a simulated air stream is shown . a first gas cylinder 30 a supplied a n2 gas stream which was passed through a water - filled bubbler 40 . this stream was mixed with another dry n2 gas stream supplied by a further gas cylinder 30 b to deliver a water vapor feed with a certain concentration to a feed inlet of the cny - modified composite membrane module 100 . the desired water vapor concentration were achieved by carefully adjusting the flow rates of the n2 streams using flow controller 50 , flow meter 60 and pressure gauge 70 as well as humidity measurement probe 80 . the feed flow rates were varied from 1 - 5 ml / min and the water vapor concentrations were varied between 4 , 000 to 40 , 000 ppm . a vacuum pump 120 was connected to the shell - side of the module 100 through a cold trap 110 immersed in a liquid nitrogen container . the highly hydrophilic membranes allowed only water vapor to pass through the membrane . the water vapor was collected into the cold trap 110 . a bubble flow meter 130 was used to measure feed outlet flow . the concentration of water vapor in the feed and collected samples was calculated . now referring to fig3 a - 3c , sem images of the surfaces of a plain pp substrate , sap and cnim - sap are shown , respectively . fig3 b shows a defect - free dense sap layer over the hydrophilized pp substrate . the wrinkled surface of the cnim - sap in fig3 c indicates the presence of cnts embedded into the polymer matrix . with reference to fig3 d , the cross - section of the cnim - sap layer clearly shows uniform dispersion of cnts in the sap matrix . now referring to fig4 a and 4b , thermal degradation behavior and thermal stability of the cnim - sap was studied by thermogravimetric analysis ( tga ). fig4 a reflects the tga curve of the composite membrane . it is clear from fig4 a that the membrane is quite stable at moderate temperature . the tga curve of the composite membrane showed its first weight loss stage occurring at 275 ° c . followed by a sharp decomposition at 400 ° c . fig4 a also demonstrates a slight increase in thermal stability for the cnim - sap membrane due to the presence of cnts in the polymer matrix . fig4 b shows the dsc curves of the composite membrane . a relatively high glass transition temperature was observed at 237 ° c . now referring to fig5 , the change in hydrophilicity of the unmodified and modified pp substrate is presented . the contact angle value of unmodified pp membrane ) ( 92 . 5 ° clearly demonstrates the hydrophobic nature of the membrane . after hydrophilization , the contact angle reduced to well below 90 ° for the modified pp substrate . the sap and cnim - sap coatings over the modified pp substrate exhibits a similar type of enhanced hydrophilicity and the contact angle reduced further to about 28 °. the transport of gas through a dense polymeric membrane is usually governed by a solution - diffusion mechanism . wijmans , j . g . ; baker , r . w ., the solution - diffusion model : a review , j . membr . sci . 1995 , 107 , 1 - 21 . here the gas molecules preferentially sorb onto the membrane surface which is followed by the diffusion under a concentration gradient . the rate of transport of solute across the membrane can be expressed in terms of flux , which can be expressed as : the reciprocal of k is the overall resistance to mass transfer , which is the sum of the liquid boundary layer resistance ( 1 / k l ), membrane resistance ( 1 / k m ), and vapor boundary resistance ( 1 / k v ); the partitioning of water vapors on the membrane and its desorption on the permeate side may be considered instantaneous and the vapor phase boundary layer on the permeate side may be assumed to offer negligible mass transfer resistance . dutta , b . k ., sikdar , s . k ., separation of volatile organic compounds from aqueous solutions by pervaporation using s - b - s block copolymer membranes , environ . sci . technol . 1999 , 33 , 1709 - 1716 . therefore , the maximum mass transfer resistances are attributed to the boundary layer at the membrane - air interface and the diffusion through the membrane . the liquid boundary layer resistance depends upon the feed flow rate , viscosity , diffusivity , whereas the membrane resistance is a function of the membrane thickness , temperature , and permeability of the specific compound . dutta , b . k ., sikdar , s . k ., separation of volatile organic compounds from aqueous solutions by pervaporation using s - b - s block copolymer membranes , environ . sci . technol . 1999 , 33 , 1709 - 1716 . as the concentration of water vapor in the permeate side is negligible , the overall mass transfer coefficient ( k ) can be described as , the efficiency of the process was quantified based on the removal of water vapor from the air stream and was expressed as percent water vapor removal (% r ) the rate of water vapor transport across the membrane can be expressed in terms of flux j w ( gm - mol · cm − 2 · min − 1 ) now referring to fig6 , the specific sorption capacity of the water by cnim - sap as a function of relative humidity at different temperatures is depicted . the presence of the small amount of cnts did not alter the sorption characteristics of the sap . from fig6 it is also observed that the increase in temperature did not significantly alter the sorption capacity of the cnim - sap . this is a surprising and interesting feature because under normal circumstances the sorption decreases with increase in temperature , but that was not observed in the temperature range studied . the ideal and linear sorption behavior as described by henry &# 39 ; s law of adsorption can be altered dramatically by specific interactions with the polymer and among the solute molecules . it is evident from fig6 that the sorption isotherms closely resemble rogers type - iii sorption . these types of isotherms are observed when water molecules serve as swelling agents for the polymer , and follow the flory - huggins principle where the solubility coefficient increase with pressure . see , flory , p . j . principles of polymer chemistry , cornell university press , ithaca , n . y ., 1973 ; shafee , e . e ., naguib , h . f ., water sorption in cross - linked poly ( vinyl alcohol ) networks , polymer 2003 , 44 , 1647 - 1653 . here the mutual interaction of the sorbed water molecules leads to the formation of clusters within the membrane matrix . see , roger , c . e ., permeation of gases and vapors in polymers , j . comyn ( ed . ), polymer permeability , elsevier applied science , new york , 1985 , 32 . now referring to fig7 a - 7b , water vapor removal was evaluated as a function of feed concentration at different temperatures . the water vapor percent removal ( fig7 a ) and flux ( fig7 b ) increased with relative humidity . this was attributed to the enhanced driving force for mass transfer . in the temperature range evaluated , the increase in water vapor removal and flux was attributed to the increase in diffusion coefficient . in typical solution diffusion models the permeability is given as a product of solubility in the membrane and diffusion coefficient . under normal circumstances the former is known to decrease with an increase in temperature , see , castro , et al ., the analysis of sorption data of organic vapors in polymeric membranes through novel theories , j . membr . sci . 1996 , 113 , 57 - 64 , but as seen from fig7 a and 7b that was not the case . therefore , permeation was directly related to diffusion coefficient . as already mentioned , the sorbed water molecules formed clusters within the membrane matrix and this prevented their rapid permeation . however , in the cnim - sap the transport of the water vapor could take place in the cnt domains where the cnts allow the water vapor molecules to adsorb - desorb easily and migrate to the permeate side . in short , the cnts can break up the water clusters and facilitate faster water vapor transport . the enhancement in the percentage water extracted by the cnts is shown fig7 c . a significant improvement in water vapor removal was observed and the enhancement increased with temperatures and was as high as 45 %. at high humidity more water clusters were formed in the sap and the cnts were more effective in breaking them up which led to higher enhancements . now referring to fig8 a , water vapor flux is shown as a function of the inlet air flow rate . it was observed that the flux increased with the feed flow rate . however , with reference to fig8 b , the percent removal of water vapor reduced with an increase in flow rate due to lower residence time . it was also observed that at a given flow rate the flux and percent water removal increased with increase in temperature . now referring to fig8 c , the variation in enhancement in the presence of cnts at different feed flow rates and temperatures is shown . the cnim - sap exhibited higher enhancement at increased temperature . the increase in flow rate led to a reduction in boundary layer formation on the membrane surface . since the cnts were embedded in the matrix , they did not affect the boundary layer formation . consequently the enhancement in water removal in the presence of cnts was not affected by feed flow rate . tables 1 a and 1b present the mass transfer coefficients as functions of water vapor concentration and feed flow rate , respectively . at low flow rates the overall mass transfer was controlled by diffusion through the boundary layer . with increase in flow rate increased turbulence and reduced the boundary layer at the membrane interface leading to higher mass transfer coefficients . there was only slight increase in mass transfer coefficient with relative humidity . the overall mass transfer coefficients also increased with increase in temperature as the diffusion coefficients increased . the tables also present the enhancement in mass transfer coefficients for the cnim - sap in comparison to the membrane without cnts . unmodified membrane as a function of feed flow rate ( at 68 % rh ) now referring to fig9 , the stability of the membrane in terms of water vapor flux and % water vapor removal was plotted against time . fig9 shows that the membrane was quite stable for long term use . with reference to fig1 , mechanistically speaking , without being confined to a single theory , the permeation of water vapor molecules in the cnim - sap polymeric membranes disclosed herein occurred through several successive steps . initially , the moisture in the feed absorbed on the membrane surface and in the free spaces within the membrane . these absorbed molecules then diffused across the membrane to the permeate side . the strong interaction between water and the sap is an important consideration . the water in sap membrane can be classified as bound , semi - bound and free water . see , liu et al ., modified acrylic - based superabsorbents with hydrophobic monomers : synthesis , characterization and swelling behaviors . j . polym res ( 2011 ) 18 : 897 - 905 . the sap molecules strongly interact with the “ bound water ” and physically restrict its permeation by creating a gel . the portion of water molecules that does not participate in hydrogen bonding with polymer is termed “ free water ”. the amount of free water depends upon the water - polymer interactions and the ability of the water to form clusters within the free space of the membrane . see , qu et al ., novel ph sensitive chitosan hydrogels : swelling behavior and states of water , polymer 2000 , 41 , 4589 - 4598 ; carlsson , et al ., hydration of ethyl hydroxyethyl cellulose , polymer 1986 , 27 , 431 - 436 . the cnts interact with water via multiple mechanisms . the presence of hydrophobic cnts reduces hydrogen bonding among the water molecules and with the sap . see , bekyarova et al ., cluster - mediated filling of water vapor in intratube and interstitial nanospaces of single - wall carbon nanohorns , chemical physics letters 2002 , 366 , 463 - 468 . the cnts show high hydraulic conductivity due to liquid slip at the solid - liquid boundary , subcontinuum alteration of dipole orientation and apparent reduction in liquid viscosity on the cnt surface . in short , the enhancement of flux in cnim - sap is due to cnts ability to influence water - polymer interactions , leading to the generation of more free water that can be easily transported along frictionless cnts . the highly hydrophilic cnim - sap was successfully employed to harvest water vapor from air . the presence of cnts led to higher amounts of water vapor being extracted which increased with relative humidity . the cnim - sap demonstrated several advantages over a membrane without cnts including enhanced water vapor removal as high as 52 %, and 44 % enhancement in mass transfer coefficients . the water vapor flux and the mass transfer coefficient of the membrane reached as high as 28 . 31e - 9 gm - mol · cm − 2 · min − 1 and 8 . 14e - 7 respectively . thus the cnim - sap membranes may be successfully employed in various water harvesting applications . although the systems and methods of the present disclosure have been described with reference to exemplary embodiments thereof , the present disclosure is not limited thereby . indeed , the exemplary embodiments are implementations of the disclosed systems and methods are provided for illustrative and non - 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