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    Teacher efficacy is a simple idea with significant implications. A teacher’s efficacy belief is a judgment of his or her capabilities to bring about desired outcomes of student engagement and learning, even among those students who may be difficult or unmotivated (Armor et al., 1976; Bandura, 1977). This judgment has powerful effects.

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    Teacher efficacy is a simple idea with significant implications. A teacher’s efficacy belief is a judgment of his or her capabilities to bring about desired outcomes of student engagement and learning, even among those students who may be difficult or unmotivated (Armor et al., 1976; Bandura, 1977). This judgment has powerful effects.

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    © All Rights Reserved
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    2 views10 pages

    Combustion of Chemical

    Uploaded by

    Abbas Gholami
    Teacher efficacy is a simple idea with significant implications. A teacher’s efficacy belief is a judgment of his or her capabilities to bring about desired outcomes of student engagement and learning, even among those students who may be difficult or unmotivated (Armor et al., 1976; Bandura, 1977). This judgment has powerful effects.

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    (2) oy os) my) wo en @ 6s) (58) 66) United States Patent Ho et al. SUPER-TYDROPHOBIC HIERARCHICAL STRUCTURES, METHOD OF FORMING ‘THEM AND MEDICAL DEVICES INCORPORATING THEM Inveators: Audrey Yoke Yee Ho, Crescent (SG) Isabel Rodriguer, Singapore (SG) Hong Yee Low, Botanni (SG); Emma Kim Luong-Vn, Singapore (SG) Sriram Natarajan, Hillsborough, ND (US), Noha Elmouelh, Randolph, NI (US); Kevin Cooper, Flemington, NI (US); Chee Tiong Lim. Singapore (SG) Assignees: Depuy Synthes Produets, LLC Raynham, MA (US), Ageney for Science, Technology and Research, Connexis (SG) Notice: Subject to any disclaimer, the team ofthis pateat is extended of adjusted under 35 USC. 154(b) by O days Appl. No: 19/441,496 Filed: Apr. 6,2012 Prior Publication Data US 20130265761 Al Oct. 10, 2013 (2006.01) 264/293; 264/219; 264334 Field of Classification Search spc 264/219, 298, 334 ‘See application ile for complete vearch history. References Cited U.S. PATENT DOCUMENTS 4.256693 aot 8 SDSL Kondo eta Bios Dejietal (10) Patent No. 4s) Date of Patent: ‘US008926881B2 US 8,926,881 B2 jan. 6, 2015 4753776 A 61986 Hillman a Foros A 1990 Lenmar etal Sites A Lise Wilke S246AS1 A 9:1903 Tresony et a S2ae666 A 11993 Vogler eal SSmcs19 A 1904 Dunn etal SBaQ6iL A 11904 Vogler ea S4SS009 A LO1905 Vogler ea (Continved) FOREIGN PATENT DOCUMENTS Dr 4126877 1 ti992 Comtinved) OTHER PUBLICATIONS ‘Yow Loe a, “Fabicaton of Hierarchical Sutures on a Ply rer Sure to Minie Natural Supetydophobie Sutioet Advanced Materials vo. 19, pp 2350-2335 (2007) (Continved) Primary Examiner —Jellrey Wollschlager SwellaYi Assistant Examiner (74) Attorney, Agent, of Firm — Roberts Mlotkovwski Saran & Cole, BC on ABSTRACT Synthetic polymer substrates comprising a hierarchical sur face stricture of multiple domes ad multiple pillars on sid domes, wherein said substrate isa synthetic polymer film, sid comes have diameters in the range from about 5 jum %0 out 400 pm, heights in the rage from about 2.5 um and ‘bout 500 pm, and said pillars have diameters ia the range from about 20 nm to about $ jum and aspect ratios of from about 2 to about 50, and methods of making and using them. 16 Claims, 2 Drawing Sheets US 8,926,881 B2 Page 2 66) References Cited USS. PATENT DOCUMENTS $5272 A 10/1906 Root etal So25319 A ‘390% Koln cal 6260.72 Bi 7/2001. Mulhauser a O308S7L BI 42002 Chisel eal ORGS BL 6.2002. Berwada cal 1485503 B2 112002 Jacobs ea S38284 BI 10.2005 Rowers et al 6720.49 BI 42004 Cuts eal SS72A99 B2 42005 Fearing el Sb18697 B2 7005 Loper eat Tinrs204 B2 72006 Debrow TAOS? BD 42007 Agra ta 7331.19 B Ory etal Tate Bw Sagota ea. THA8223 BD Schubert et 7780233 Be Antic etal Toss Shimp cal. Prete-Bloom oa 20030208888 AT 11/2003 Fearing eal. aoouoores2? Al '4/2008 Iago a 20080125265 AL 7/2004 Miyauchi etal doosoloess> Al_ $2008 Ikea a00so1si629 AI* 2005 Jape al 438780 20060005362 AL 1/2006 Art eal donaoo47s4 AL_ 22006 Schubert aops0o7s724 AL* 4/2006. Bhushan eta sean dooworssoes AL 7/2006 Feybara ta 2npe0204738 AL 9/3006 Dubrow eta donyonz796? AL 102007 Sakaino eal a0070299842 AL 122007 Mahim doowol24e46 AL 15/2008. Dis-Qui a doowOaT7IND AL 9.200% Deyeetal 20080241512 AL 102008 Borstal 20080241925 AL 102008 Leeeea doowookioss AL 11/2008 Livme 20090130872 AL $2008 Fu eta 2ooostsss3 AL 12/2000 Van alten zoro.09Ko09 AL ‘4/2010. Repeat 20100137903 AL 62010 Leet 2oLvooris6s AL 12011 Kampet al 2OLLO1G0N69 AL 62011 Duchet a ‘O172760 AL 72011 Anderson DOLLOIT286 AL 72011. ‘Bhashan eta dovorkeast AL U1 2011 Liveral. 20110293667 AL Baksh a dowdoos2244 AL Natarajan eal 30120143228 A Natarajan etl So120RS161L AL 102012 LuoogeVan et 20120302427 AL 11/2012 Elmoucthi ea ao120302465 AL 11/2012 Elmouelhi eta. 2o1¥0172927 AL 72013. Natanjan ea 20130206830 AL 2013. Naamjan ea 201S0267ESO AL 102013 Lvong-Van et 20130288225 AL 102013 Elmovethi ea FOREIGN PATENT DOCUMENTS. BP isos 52004 ° aooettonss 62004 ae 201322613 A 112013, So Tos A 102013 wo oosssne © '9:3000 wo okomte® AL 122008 WO 2008008303 A211 2004 wo oosa3ti97 13 2006 WO SLY AL A 2uo8 WO 2008076390 A 6 2008 WO donwtar6ay AL $008 wo pomonoLL A? 22009 wo 2om025045 3 2009 WO Somers aL 5.2000 Wo do1gasett AL 112010 Wo dorworeos? AL "32011 WO 201202085 AL 32012 Wo — Wo2120%570 AL 32012 wo "O3ni3srIT4s a2 112012 WO — worIdHe~s2 a2 112012 wo "Porte At '72013 WO —Wo2I3I02085 AL 72013 Wo" O3nnsienog AL 102013 (OTHER PUBLICATIONS ‘young Je Cha eta “et of Replicate Polymer Substrate with Totus Surface Srcture on Adipse-Derived Stem Cell Behaviors" ‘Macromolecular Biossiene, ol 1p. 1387-1363 2011), “Takashi Vangisita eal, "Anti-Reection incurs on Lenses by ‘Nanoimprinting Using Ordered Anodic Porows lumina”, Applied Physics Express 2p. 022001-1-022001-3 (209) Anza). Schulte tay “Hierachicaly Stoctred Superhyrophobic Flowers with Low Hysteresis ofthe Wild Pansy (Viola Tricolor) ‘New Design Principles for Biomimetic Materials, Beistein J. Nanotechnol, vol. 2.pp. 228-236 011). [Bharat Bhushan cal “Micro-, Nano- and Hirchical Structures for Supethyophobiciy Self-Cleaning and Low Adbesion”, Philo sophia Transat ofthe Royal Society. (2009) 367 gp. 1631- 1672, Downloade from rt royasoeesypublshing org on Mar, 2 2012, Sit, "High Aspect Ratio Polymer Micro/Nano-Structue Manus turing using, Nancembossng, Naaomolling and Directed Self Assmbly"\ IEEE ASME Advaneod Mechatronics Conference Kobe, Sapen, Jul 2003 (pages). Teovgen ctl "Nano-ecuring of poy (octyl methacrylate) ply rer ting plasma proceses and applications in wetng conto and protein adsorption", Microelectronic Engineering 86 (2009), p. Tana-tar7 ‘Vachoponiou tal Eft of surface nanosrictring of PDMS on ‘wfting properties, iyophobic recovery and poten adoro’ ‘Microelectronic Engineering 86 (2009), pp. 1321-1324 Ocehieln ct, "Osygen-Pasina-Feat Polypropylene Interest with Air, Wate and Fpoxy Resins: Pur 1 Air and Wate, 1991 ural of Applied Polya Science 42, pp. 81-889 ‘Gera «ay "Surface medications of polypropylene membranes ‘sa for blood tation" 2011, Polymer, $2, pp. 1223-1235. Yoong Won al, “The Fabrication of Protein Nano Arrays Using ‘3.Dimensional Plastic Nanopillar Pairs". Nanoscience and Nanotechnology ol 1p. 4231-4258 QO), Ning Shao etal. “Seiforenized Polymer Agaregates with 2 Biomimetic ‘Hierarchical Stuctre an Hs. Soperkyrophabic fet, Cel Biochem Brophy, vl 49, pp. 91-97 007, hart "Bhushan et aly SelCleaning Efficiency of Anil Supethydophobie Surfiew” Langit, vo. 25, No. 8, pp. 3240- 324812000} 5m Shi eal, “Towns Bionspird Superhydropbobic PlyL ctv acid) Surtees Using Phase Inverson-Based Methods", Biinspir- thon & Biomimetics 9h 3. pp. 16 2008), ‘Yong Chte Jung cal "Weting Behavior of Water and Oi Droplets “The-Phase Inleices for Hydrophbicitypiliciy and Oophobicty piiciy”, Tanga, ol. 28 (24), pp. MU6S-14173 (2008), Srimm Natanjan, PCT No, PCTUS 2011 ‘uiey Yoke Yee Ho, US. Appl. No, 13441 496, ied Ape 6, 2012. US. pl No. 12871348; le Aug. 30,2010 US. Appl No. 10340,331 ied De. 29,2011 US. Appl No. 18340408, filed De. 29,2011 US. Appl No. 1435544, ied Mar 30,2012 US. Appl No. 18116721, filed May 26,2011 US. Appl No. [861,539 p 6, 3012 US. App No. [8 458825, filed Ape 27,2012 Anthony G. Grist, "Bromatvia-Ceatered Infection: Mirobial ‘Adhesion Versus Tissue Integration”, Science, vl. 237, pp. S88- 1398 4987) International Search epot for International Application No, PCT! LUSDOILO#85E4 dated Feb 20,2012 Inenaionl Search sept fr International Application No. PCT [US20120072081 dated Mar 12,2013 2011088 584 Filo Ane 2, US 8,926,881 B2 Page 3 66) References Cited OTHER PUBLICATIONS Sriram Natarajan, U.S. App. No. 12871.745, led Aug, 30 2010 Noha Hmovelhi US. Appl No. 116.721 led May’ 26,2011 Stam Natarajan, US. App. No. 13340331, Hed Dee 29, 201 OS. Ap No. 13340405, fled Dee 39,2011 Tuoap-Van, US. Ap No. 133844, Ml Ma. 30, 2012 Emma Kim Luong-Van, US. Appl No. 13 bu? Noh Elmovethi, US. App. No. 13458.825, fed Apr. 27,2012, Stars Natarajan, US Appl No. 1393285, Hed Dec 28,2012 Sita Nata US. Appl No. 13841861, Hd Ma 15,2013. Route, als “Toree Mapping in Epielal Cell Migration, pp. 230002305, PNAS, Feb 18,2008, vol 102, No.7. ‘Oxford Dictionary Online Denton of “Cylinder” Intemational Search Report for PCTI'S2012039256 date Ma. 5, Te ‘Wan Y eta “Characterization of surface propery of poy (ate ceovsycolde)allerosypen plasma teamen!, Biomater, avi Science Publishers vol 25, No. 19, Ag, 30 pp. AT77-A7R Fann Wei, et al InBivence of surface weal om competitive tein adsorption anna attachment of ones Cmptive Protsin adsorption and inl esll attachment Biome Mater als nstte of Physies Pushing, vol, No. 4, Aug 1, 2009, p 4502 Tsougen K eal, "Mechanisms of oxygea plasma nanoexturingo orgie polymer sutacer: From sable super hydrophilic to super hyophobiesurfices, Langu, American Chemis Society, ¥0 25, No 19, Oct 6 2009, pp 1748-11759 “Messina G MLct al, “A iuitechnique study of prefect po- ‘sin aleonion oa hydrophobic an Bydophle pasia-modied pyr sacs” Colloids and Sortaces.B, Biointrfaes vl. 70, No Apt 1, 2008, pp 7:8. 1.599, led Ape 6, Chen HL ct al, “The effet of surface micotoposraphy of poly (dimethytsiloxane) onprotein asm, placetand cell athesion" Colloids ad Surtace 1, Bivitrfaces vo. 71, No 2a 1, 200, pp. 275-281 Definition of “Integral”, Meriam-Webster Dictionary online, pp. 1-3, Aeeosod Oct. 18,2013 ‘Stitam Natarajan, US. Appl No, 1'871,745 fed Aug. 30,2000. Noha Elovethi US. Appl. No, £116,721 fied May 26,20 Sriram Natarajan, PCT No, PCTUS2011 088584 Filed Avg. 22, 2011 Sriram Natarajan, US. Appl. No, 13/340.331 fled Dee. 29, ‘Noha Elmoveli US. Appl. No, 11740405 filed Dee 29,201 Emma Kim Lung-Van, US. Appl No. 13-84 ed Mar. 30, 2012 Emma Kim Luong-Van, US. App. No. 18 44,539 filed Ape 6, 2012, Noha Elmovelhi, US. Appl No, 13488825 filed Apr 27,2012. ‘Noha Elmouelhi PCT No. PCT'US20121059286 file! May’ 12.2012. Sriram Natarajan, US. Appl. No. 137730289 fled Dee. 28,2012 Stam Natarajan, PCT No. PCTUS20I2072081 fled Dee. 28, 2012 Seam Natarajan, US. Appl No. [3841 S61 fled Mar. 15,2013 ‘Noha Elmouelhi, PCT No. PCT US201 9038007 fled Ape 33,2013 Audrey Yoke Yee Ho, US. Appl No, 1139673 filed Dee. 23.2013, SD. Lee, "Surfice Modification of Polypropylene Under Argon and ‘Oxygen RF-Plsra Conditions” Plasmas and Polymers 2, No. 3, Sep. 1 1999. pp. 177-198 Inertaional Search Report for PCT'US2013 038007 dated un. 18, 2018 Sezer al, "Rigidity driven growth and migration of epithelial ec ‘on microsinetured anisotropic sbsrates, PNAS, vol. 104, No.2, pp. S281-8286, May 15,2007 * cited by examiner U.S. Patent Jan. 6, 2015 Sheet 1 of 2 US 8,926,881 B2 U.S. Patent Jan, 6, 2015 Sheet 2 of 2 US 8,926,881 B2 FIG. 3A FIG. 3B FIG. 3C FIG. 4A FIG. 4B FIG. 4c US 8,926,881 B2 1 SUPER-HYDROPHOBIC HIERARCHICAL ‘STRUCTURES, METHOD OF FORMING ‘THEM AND MEDICAL DEVICES INCORPORATING THEM. FIELD OF THE INVENTION ‘The present invention relates to polymer-based structures having shapes ane! mechanical properties that induce super- hydrophobicity BACKGROUND OF THE INVENTION 1k is well known that hydrophobicity may improve the ‘mechanical properties ofa surface. One the crucial surface properties for materials in micro/nanoscale applications is on-wetting or hydrophobicity. Creating hydrophobie sur- aces on materia is desirable in some applications, because these surfaces cause water to Nov away fom the suriee, thereby preventing the buildup of liguid on the surface Hydrophobic surfaces are also desirable du to their sel- ‘leaning properties. These surfaces repel liguids, they resulting in liquid and contaminating particles Rowing away from the surface Wetting is characterized by contact angle, which is defined as the angle berecen the solid and liquid surices. IF ‘liquid wets the surtiee, the vale ofthe contact angle is 90° ‘or less (refered to as wetting Tiguid), whereas ifthe liquid ‘does not wet the surface refered to as non-wWettng liquid oF hydrophobic surface), the value of the contact angle ranges between 90° and 180°, surlice is considered superhydno- phobic, ifthe contact angle has a range of between about 150° to 180" ‘Biomimetics has played roe in the development of new surfaces, Biomimetics, which comes from Greek word “biomimesis” meaning to mimic life, deseribes the stady and simulation of biological objects with Jesced properties. To that end, scientists have studied natural surfaces that are ‘extremely hydrophobic, in order t repmodnce these proper. ties on artificial surfaces. Among these surlaces studied are the leaves of water repellent plants such as Nelumo nucifera (lows). At least two surlace characteristics are believed 10 produce water repellent propetieson these surfaces Fist the surface of the leaves is usually covered with a range of df= Trent waxes made roma mixture of krge bydrocarhon mol- ‘ecules, measuring about I nm in diameter, that are strongly hydrophobic, Second, the surface is very rough due to s0- called papillose epidermal cells, which form asperites oF papillae, The surlace of the lotus leaf generally has pyramid shaped! sperities that are spaced afew ym from one pyramid tip lo another pyramid tip. Drops of water substantially on- tact only the tips or peaks ofthe pyramids so that the contact ‘ea oF Water fo aurfae is minuscule relative to water drops ‘contacting a miero smooth surface. The reduced contact sr face area results in avery low adhesion between the water drops and the miero-rongh surface. ‘Various methodologies have been developed for design snd formation of super-hydrophobie sures which mimic that ofthe lotus leat, For example, US, Patent Publication No, 200610078724 discloses design criteria for lotus lea? mimetic structures, and suggests a number of methods whieh ‘could be use to make such structures, including etching and ‘embossing processes, coating processes, shaping processes using appropriately strctored molds, polishing processes, photolithography, solvent or vapor deposition, eleetroplting, 2 electrowetting, plasma processing, warm-water processing, ‘and high temperature sintering However, no detailed method ‘of formation is disclosed, In “Fabrication of Hierarchical Stractures oa a Polymer Surface to Mimic Natural Superhydrophobic Surfaces", Advanced Materials, vo. 19, pp. 2330-2335 (2007), Yawon Lee et al. disclose a fabrication process consisting of three processes: photolithography, aluminum etching‘anodization ‘and polymer replication, wherein well-defined microstme- ture pattems were transfered onto the surface ofan alum ‘oum sheet by photolithography using a photoresist an shadow masks, followed by etching and anodizing of the sluminum surface o form a negative, hierarchical replication ‘template, o which was applied a high density polyetiylene substmte. The HDPE substrate was forced into the negative femplate under heat and pressure, and subsequently peeled from the template to produce lots leaf mimetic hierarchical polymeric strictures U.S Patent Publication No, 2008/0217180 discloses a sur- ‘ace comprising a mirostructure that reduces adbesionandto ‘method for producing said microstructure. Microstructures ofthis type that reduce adhesion are known and are used, for example, to configure self-cleaning surfaces that use the Lots effect, According to the invention, the surface i pro- duced electrochemically by means of reverse pulse plating. the known microstructure being fist produced and a nano- structure that is overaid on the microstructure is produced st the same time or ina subsequent step. 'ULS. Patent Publication No, 20100098908 discloses an anielehaving a nanotextured surface with superhydrophobic properties, comprising an aray of vertical tabs, formed by photolithography. Tn “Effect of Replicated Polymeric Substrate wih Lotus Surface Srueturean Adipose-Derived Stem Cell Behaviors", ‘Macromolecular Bioscience, vo. Vl,pp. 1387-1363, Kyoung Je Cha etal. disclose fabrication of polystyrene substrates ‘with lows leaf surface structures by electroforming nickel ‘onto @ natural lotus lea to form a mold, fllewed by hot embossing with polystyrene. U.S. Patent Publication No. 2011/0177288 discloses meth- fods of making superhydrophobie siruetures comprising ‘depositing polymer mold ont silicon surface comprising a plurality of microasperities, removing the polymer mold aftr the polymer mold has hardened, depositing a liguid ‘epoxy resin int te polymer mold, forming a microstructure ‘with a plurality of microasperties by separating the epoxy resin from the mold after the epoxy resin has solidified, and orming a superiydeophobie structure by depositing aplural- ity ofalkane nanoasperties onthe microstructure in the pres- ence of solvent vapor Tt would be desirable © provide a simpler method for {formation of hierarchical, biomimetic stractoes, SUMMARY OF THE INVENTION ‘The present invention relates to a method of making a syniietic polymer substrate comprising hierarchical surface structure of multiple domes and multiple pillars on said ‘domes, comprising forming anatray of dome-shaped depres- sions, each having a diameter anda depth, in a solid vemplate substrate; forming a porous surface on said dome-shaped depressions, wherein sad porous surfaces foamed of amate~ rial diferent from that of said sold template substrate; and ‘contacting sid porous surface with a synthetic polymer ther ‘moplastic film binder lempersture and pressure conditions sulficient to cause said thermoplastic to low into pores of said US 8,926,881 B2 3 porous surface and said dome-shaped depressions to for ‘imprinted film having seid hierarchical surface steeture TInanother embodiment, the present invention is directed to 1 synthetic polymer substrate comprising a hierarchical sur- Tce structure of multiple domes and multiple pillars on sid domes, wherein said substrate is a synthetic polymer fil, said domes have dismeters in the range from about 5 jum bout 400 an, heights inthe range fromabout 2.5 um‘ about 500 jum, and said pillars have diameters in the range from about 20:nm to about 5 ym and aspect ratios of Irom about 2 tw about 50, Ina further embodiment, the present invention is directed ‘oamedical device, comprising substrate having synthetic polymer film comprising « hierarchical surface siructure of ‘tiple domes and multiple pillars on said domes, wherein said symthetic polymer film is a thermoplastic polymer film, said domes have diameters in the range from about 5 jum about 400 um, heights in the range fom about 2.5m to about 500 jum, and said pillars have diameters inthe range from 2 about 20 nm to about 5 um and aspect ratios of Irom about 2 to about $0, BRIEF DESCRIPTION OF THE DRAWINGS. FIGS. 14 and 1B show PE-SEM images of top and eross- sectional views, respeetively, of a porous anodic alumina (PAA) template prepared by the inventive process. FIGS, 2 and 28 show FE-SEM images of polypropylene hierarchical lous leatlke structures. FIGS, 3A.3C show images of water contact a surements on domed structures (3) andon domed-structures having lots lea-like topographies (3B, 3C). FIGS. 44-4C show FE-SEM images of lotus leaflike structures having 400 jum domes and 0.8 um, 1m and 3 yma diameter pila strvctures, respectively. DETAILED DESCRIPTION [Naturchs created surfice structures that have potential for biological applications. However, these structures are com plex mixtures of miero- and nano-sized shapes and features. To fabricate these on polymers of interest is a challenge that needs to be adkdressed, Inorclerto address tis challenge, fons Jeaf mimetic surfaces comprising hierarchical strocture of a micrometer sized dome anda pillared nanosurface have been {abricatedby a one step nanoimprinting process ona polymer using a specially prepared hierarchical template. none embodiment, the invention i directed toa process to make hierarchical surface features om a polymer substrate The process involves making a surface with domeslike fese ‘ures by lithographic means on a silicon wafer followed by ‘etching, or by micromachining the dome-lke Features into 3 substrate, followed by placing a porous template onto the surface. In either embodiment a polymer film is subsequently pressed into the pore/depressions thereof to form the hierar- ‘Chica structure onto the surface of the film. Generally, the process ineludes forming an aray of dome shaped depressions, each having a diameter and a depth in & fold template substrate, followed by foaming a porous str- face on stid dome-shaped depressions, wherein said porous surface s formed of a material different from tha of sail solid template substrate, Subsequently the combined porots sti ‘ace and solid template substrate is contacted with a synthetic polymer thermoplastic film under temperature and pressure ‘conditions sufficient to cause the thermoplastic polymer to 0 o 4 flow into both the pores and the underly shaped ‘depressions to form an imprinted film having a hierarchical surface structure, ‘The dome-shaped depressions can have diameters in the range from about Sy to about 400 un, depts inthe range from about 2.5 jm to about S00 ym, Advantages, the Pitch (i. the center to center distance) between the dome- shaped depressions is approximately equivalent (i.e. on the same onder of magnimde) to theie chosen diameters. The pores in the porous surface ean have diameters ia the range {rom about 20 nm to about S jn and aspect ratios of from shout 2 0 about 80. ‘Depending othe desired relative dimensions forthe hier- archical structure, wo diferent embodiments bave been ‘developed for forming the mol The inital template can be prepared by standard photo! thography and micromachining techniques in silicon. These techniques allow one o proce a wide range of features with igh dimensional precision and reproducibility, Ditferes structural featurescan beused asafist eve of hierarchy such as lens, domes, gratings ete with circular or square shapes. The template can be made on or replicated om to other mate rials like quart, fuse silica, nickel. Hence, ths fabrication Approach allows greater flexibility in terms of stractralfea- tres andlor material for the first level of hierarchy template (On the selected template, an aluminum film is deposited ‘through a sputtering or evaporation processes, The AL film ‘ill conform tothe festores covering the entre surface ofthe fistlevel template, Upon anodizing ofthis AH film nanosized pores are reated onthe film, The procesé can ereate norm ‘nd well-defined height for the hierarchical nanostructures since it uses an Al layerto create these structures alike other processes. The snadization process has a natural etch stop on the non-A substrate. In fist embodiment of the process, the solid template substrates asilicon water and said dome-shaped depressions are formed by lithography and dry etching. A porous surface is formed by depositing an aluminum film on the dome- shaped depressions snd anodizing the aluminum fiz, which ‘ets to form pores i the aluminum film. According to this embodiment, the dome-shaped depres- sions can have diameters inthe range from about 10 yun 10 bout 40 um, depths inthe range rom about um toabout 20 um, andthe pores can have diameters in the range from about 20m to about $00 nm, or even from about 200 nm to about 400 am, and aspect ratios of from about 20 about 50, rom ‘shout 2o about 25, oF from about to abou 28, or From abut 20 about 5. Advantageously, the pores can have an average pore diameter of about 200 nm and aa average depth of about 500 nm ‘After te polymer fil las been flowed into the mold, th process futher comprises de-molding the imprinted hierac al structured flm by peeing it fom the sold template sub- Ina Second embodiment of the proces, the solid template substrate is a metal substeate and said dome-shaped depees- ions ae formed by micromachining, Advantageously, this embodiment ofthe process does not necessarily require the use of clean room Lites. The process involves initially ‘machining thedome structures in amital substrateto form the first level of hierarchy. The size imit for this type of machine tooling isin the range of 100 um. The second hierarchical level is achieved using commercial filter membranes. These membranes are typically made of polycarbonate, and have pores running through the thickness of the membranes whieh US 8,926,881 B2 5 ‘are produced using ion track etching, The thickness of the ‘membrane is typically 20 um and the pore widths vary from 04-5 um, "The membranes inthis embodiment are fee standing track ‘etched membranes having pores therein, which are placed on. the surfce of the machined dome depressions in the solid template substeate, and freed into said dome-shaped depres- sons along with the thermoplastic polymer film, which is Positioned on top of the porous membrane, and under the same temperature and pressure conditions, ‘According to this embodiment, the dome-shaped depres- sions can have diameters in the range from about 50 ym to about 400 jm, dep in the range from about 50 um to bout 100 ym, and the pores can have diameters in the range from about 200 nm to about 3 ym, oF even from about 400 nm to about 3 jum, and aspect ratios of from about 210 about $0, oF from about 2 t0 about 25, of from about 3 1 about 25. Accordingly, de pores can have diameters inthe range frm about 0.4 ym to about 3m. ‘As stated above, the method futher comprises placing the symhetic polymer thermoplastic film onto said track etched ‘membrane, andl applying sad temperature and pressire on- ditions 1 the combination of the synthetic polymer thermo- plastic film and porous membrane, sos to force thermoplas- tie polymer fom a surface ofthe film ato the pores of said freestanding rack etched membrane, and both ofthe film and the membrane into the underlying dome shaped depressions in the metal substate Conveniently, the free standing trick etched membranes polycarbonate filter membrane, and the process further com Prisesremoving the combined polycarbonate filter membrane ‘and polymer film from the mold and dissolving the polyear- bona filter membrane with a solvent, leaving the polymer substrate comprising a hierarchical surface strueture. The solvent fr the porous membrane shouldbe selected sch that it does not affect the polymer film. For example, when the fiker membrane is polycarbonate and the syntheti polymer film is polypropylene, etrachloroethylene isa suitable sol- This fabrication process is practeal and low costa it uses ‘machined molds and commercially avsilable porous mem- branes. However, the process tools limit the fabsication ofthe hierarchical lotus lea structures to lange sizes than in the previous process. The dome size and membrane thickness red to be chosen to mateh, The dome width shouldbe larger by approximately 5 times that ofthe membrane thikness for the membrane to comply with the dome topography. Like- ‘wise, the dome sagita (depth) shouldbe larger than the ticks ress of the membrane as otherwise the pillared strctures ‘would conceal the dome structure. The inventive processes described above ean be used {0 make a synthetic polymer substrate, such as one for use on & medical device, comprising a hierarchical surfacestructureof ‘multiple domes and multiple pillars on said dames, such as wherein the substrate is a synthetic polymer film, the domes ‘can have diameter inthe range from about jm to about 400 |um, heights in the range from about 25 um to about S00 um, and the pillars can have diameters inthe range from about 20 1am to about 5 yum and aspect ratios of from about 2 to about 50, or from about 2 to about 25, ar even from about 3 to about 25, Advantageously; the synthetic polymer substrate is a ther- ‘aplastic polymer, such as one selected from the group con- sisting of polypropylene, polycarbonate and polydioxanone, ‘and the domes ean have ditmeters in the range Irom about 10 |um to about 40 um, heights in the range fom about $ ym to about 20 um, and said pillars ean have diameters in the ange 0 o 6 {rom shout 20 nm to about S00 nm, oF even from about 200 ‘nm to about 400 nm, and aspect ratios of from about 2 0 about 50, or from about 2 to about 25, or from about 3 w about 28, for from about 2t0 about 5. Advantageously, the pillars ean have average diameters oF about 200 nm and average heights of about 500 nm Alternatively, when using the mieromachining process the domes can have diameters inthe range from about 50 um 10 bout 400 um, heights therange from about SO jum to about 100 um, andthe pillas ean have diameters inthe range fram out 200 am to about 3 ym, oF even from about 400 nm to bout 3 jm, and aspect ratios of from about 2 o about 50, or trom about 2 to about 25, oF from about 3 40 about 25. Accordingly the pillars can have diameters inthe range from ‘bout 4 nm to about 3p. In this embodiment, the pillars are ‘Formed within the pores ofa track etched membrane, such as apolyearbonate filter membrane, athe pillars can be essen- tially cylindrical in shape. The synthetic polymer substrates can have a centerto-conter distance (pitch) between the {domes which s approximately equivalent tothe diameters of the domes. ‘The synthetic polymer substrates soformed havea ierar- chica steueture that renders the surface super-hydrophobic, Ihaving static water contact angles oft least about 150°, such «as from about 150” to about 163° “The synthetic polymer substrates so-formed ae integrally ‘molded, By integrally molded is meant that the structure is ‘ormed in one piece, including both its domes and is plas, from a mold, Advantageously, medical devices incorporating the syn- thatie polymer substrates described above demonstrate ben- fits suchas inhibition of fouling, ‘The invention is further explained in the description tht {allows with reference to the drawing illustrating, by Way of ‘non-limiting examples, various embodiments of the iaven- EXAMPLE 1 Fabrication Via Hierarchical Template of PAA on Silicon Silicon molds with domes of 10 um in diameter and depth ‘of Sum, pitch of 10 um were fabricated by photolithography followed by plasma etching. The molds were cleaned by ‘orons discharge to removeany organs left fom the etehing races, The substrates were then coated witha thin film of Ti fo serve as an adhesion layer on which a film of alumtianm (500 nm in thickness) was sputtered. Subsequently, the al- ‘minom film was anodized ina temperature controlled elec- teolytc solution of 0.3 MH,PO, at constant voltage of 130 t2°C. for | hour. The pores obtained were then widened by etching the barsier layer formed a the endof the anodization process in a solution of $ wt % HPO. for 90 min FIG. LA shows a top view and FIG. 1B a cross-sectional view of one of the PAA templates prepared by this process. ‘Typically the pores had an average pore sizeof 200 nm and a depth of $00 nm. Hosiover, pores ringing from 20 nm t 300 fam can be achieved varying the process parameters. The pth of the pores is determined by the anodization time. Typically it was controlled (© abtaina pore aspect ratio wf 2. Imprinting of Polymer Lotus Leaf-Like Structures ‘The prepared templates were imprinted into polymers, ‘ypieally polypropylene (PP), polycarbonate (PC) or poly” ioxanone (PDO), The templates were initially coated with a fMuorosilane release agent through vapor deposition of THLIH.2H.2H1-perfluorodecylrichlorosilane to reduce the surface energy and facilitate the demolding process. The imprinting process was performed using an Obdueatnaoim- US 8,926,881 B2 1 printer. fee sanding flm of PP with thickness of 0.5 mm was placed on top ofthe template. The template and PP sheet were heated up to 180° C. and a pressure of 60 Bar was applied for 300 s, The polymer-mold assembly was thea ‘allowed to cool down to a temperature of 90° C. before the pressure was released and demolding was performed. Denolding was performed ty physically peeing ofthe tem- plate. This template prepared with low aspect ratio (AR 2-5) ‘dimensions is reusable as the imprinted polymer readily ‘demolds from the template FIGS. 24 (2.200%) and 2B (10,000x) show an example of hierarchical Totus leaflike structures fabricated in PP. The synthetic structure includes 10 um dome structures with a Sagittal epth) of Sum and pitch of 20 ym as fist level of hierarchy and 200 nm pillar, SO0 nm in depth as second level In FIG. 2 there ean be seen elongated pillar structures at the ‘edges of the domes. This elongation takes place due to the pulling foree for demolding being applied perpensicula to the pore-pillar structures created on the side walls of the ‘domes. The pullin force caused the elongation ofthe poly’ ‘er pillars during demon probably because the polymer ‘vas not eompletely cooled EXAMPLE2 Fabrication Via Assembly ofa Hierarchical Template Initially, an aay of dome-shaped depressions were ‘machined in a metal substrate to fort the fist level of hier archy. The size limit for his typeof tooling is inthe range of 100 tm, The second hierarchical level was achieved using ‘commercial fiter membranes. These membranes are made typically in polycarbonate, and have pores running through the thickness of the membranes, which are produced using jon rck etching. The thickness ofthe membrane is typically 20 um and the pore width varies from 0.45 um, Imprinting of Polymers Lotus LeaLike Structures A porous polycarbonate filter membrane was placed “directly on top ofthe machined, dome-shaped depressio the flm to be structured was placed on top ofthe assembly ‘and brought into the imprinter system. Heat (170° C.) and pressure (60 Bar) was then applied to force the thermoplastic ‘lm polymer into both the underlying dome-shaped depres- sions and the pores of the fiter membrane. fer the imprint= ing and cooling process, the polymer film was released rom the metal mold. The PC membrane which, asa result of the process was embedded into the PP polymer, was removed by ‘dissolving it in tetrachlorocthylene, This slep results in releasing the second level of pillar structures, EXAMPLES ‘Measurement of Wetting Properties ‘The contact angle of the lotus lealike surces was mea sured. Measurements weredone intriplicate with Sand Il size droplets, and are depicted in FIGS. 3A-3C. The contact angle ofa PP surface with LO um dome sructures (113°=2.4°) indicates weak hydrophobicity (FIG. 3) However, the or responding lots ea-ike structures oF 10 wn domes with 200 rm pillars (FIGS. 38 (5 pl) and 3C (1) showed super hydrophobic characte, ‘with contact angle readings of 163215", ‘The contact angle of 400 ym PP dome structures having secondary lve pillar strictures of 8,1 and 3 um diameters ‘are shown in FIGS. 4A-4C, respectively. The contact angle ‘values were lower than the smaller nano-otos strictures ia FIGS. Band 3C, but nonetheless showed a super-hydropho- 0 o 8 bie character with contact angle readings above 150°. The contact angle for the structure in FIG, 4A was casted to be 153.1°24,6" FIG. 4B was measured to be 150,1"24.2°; and FIG. 4C was measured to be 151.0°21.3°. All patents, test procodutes, and other documents cited herein, including priority documents, are flly incorporated by reference tothe extent such disclosure is not inconsistent and forall jurisdictions ia which such incomporation is per mitted. ‘When numerical ker limits and numerical upper limits are listed herein, eanges from any’ lowe limit any upper limit are contemplated. ‘The vention being thus describe twill be apparent that the same may be varied in many ways, Such variations are not to be regarded as a departure from the spirit and seape ofthe ‘vention, and all sich modifications as would be obvious to ‘one skilled in the art are intended to be included within the scape ofthe following claims. What is claimed: 1, A method of making asyauhetie polymer substrate com- prising a hierarehieal surface structure of multiple domes and multiple pillars on said domes, comprising: forming an array of dome-shaped depressions, cach having ‘a diameter and a depth in a non-aluminum solid tem- plate substrate; orming a porous surface on said dome-shaped depres sons, wherein sal porous surlace is forme of a mate tial diferent from that of said solid template substate, and ccontseting said porous surface with a synthetic polymer thermoplastic film under temperature and presse con- sitions sufficient to eause suid thermoplastic to How into pores of said porous surface and said dome-shaped

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