US 2010O226943A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2010/0226943 A1 Brennan et al. (43) Pub. Date: Sep. 9, 2010 (54) SURFACE TOPOGRAPHIES FOR NON-TOXIC a continuation-in-part of application No. 1 1/202,532, BOADHESON CONTROL filed on Aug. 12, 2005, now Pat. No. 7,143,709, which is a continuation-in-part of application No. 10/780, (75) Inventors: Anthony B. Brennan, Gainesville, 424, filed on Feb. 17, 2004, now Pat. No. 7,117,807. FL (US); Christopher James Long, Titusville, FL (US); Joseph Publication Classification W. Bagan, Greenwood Village, CO (US); James Frederick (51) Int. Cl. Schumacher, Cumming, GA (US); A6IR 9/00 (2006.01) Mark M. Spiecker, Denver, CO B32B 3/00 (2006.01) (US) A 6LX 9/70 (2006.01) (52) U.S. Cl. .......................... 424/400; 428/141; 428/143 Correspondence Address: CANTOR COLBURN, LLP (57) ABSTRACT 20 Church Street, 22nd Floor Hartford, CT 06103 (US) Disclosed herein is an article that includes a first plurality of spaced features. The spaced features are arranged in a plural (73) Assignee: UNIVERSITY OF FLORIDA, ity of groupings; the groupings of features include repeat Gainesville, FL (US) units; the spaced features within a grouping are spaced apart at an average distance of about 1 nanometer to about 500 (21) Appl. No.: 12/550,870 micrometers; each feature having a surface that is Substan tially parallel to a surface on a neighboring feature; each (22) Filed: Aug. 31, 2009 feature being separated from its neighboring feature; the groupings of features being arranged with respect to one Related U.S. Application Data another so as to define a tortuous pathway. The plurality of (63) Continuation-in-part of application No. 11/567,103, spaced features provide the article with an engineered rough filed on Dec. 5, 2006, now Pat. No. 7,650,848, which is ness index of about 5 to about 20. 130 111 U Sea. Patent Application Publication Sep. 9, 2010 Sheet 4 of 15 US 2010/0226943 A1 Depth Spacing Width Roughness (um) (um) (um) Factor has c C O O S. s wn V Patent Application Publication Sep. 9, 2010 Sheet 5 of 15 US 2010/0226943 A1 Patent Application Publication Sep. 9, 2010 Sheet 7 of 15 US 2010/0226943 A1 FIG. 6A FIG. 6B Patent Application Publication Sep. 9, 2010 Sheet 8 of 15 US 2010/0226943 A1 FIG. 7A Patent Application Publication Sep. 9, 2010 Sheet 10 of 15 US 2010/0226943 A1 FIG. 8A 800 8500 Reduction 4 O O Patent Application Publication Sep. 9, 2010 Sheet 11 of 15 US 2010/0226943 A1 FIG. 9 Ulva Settlement VSER Gradient Studies 800 7003 v=-27.431x+ 575,34 600 R2 = 0.83 500 400 ER Patent Application Publication Sep. 9, 2010 Sheet 12 of 15 US 2010/0226943 A1 FIG. 10 Balanus amphitrite Settlement 6500 Reduction O 3 0. 2 O. 1 O FIG. 1 1A Settlement of B. amphitrite ASSay 1 1 5 1 2 48 hrs 9 6 3 Glass Smooth 2OCH 40CH 2OSK 40SK Patent Application Publication Sep. 9, 2010 Sheet 13 of 15 US 2010/0226943 A1 FIG. 11B Settlement of B. amphitrite ASSay 2 1 O O Glass Smooth 20OH 40CH 20SK 40SK 24 hrs O72 hrs FIG. 11C Settlement of B. amphitrite Assay 3 Smooth 20OH 40CH 20SK 40SK 24 hrs 48 hrs Patent Application Publication Sep. 9, 2010 Sheet 14 of 15 US 2010/0226943 A1 FG 12 50 um FIG 13 Patent Application Publication Sep. 9, 2010 Sheet 15 of 15 US 2010/0226943 A1 FIG . 14A FIG 14B US 2010/0226943 A1 Sep. 9, 2010 SURFACE TOPOGRAPHIES FOR NON-TOXC typically cuprous oxide or tributyltin, into the water. The BOADHESON CONTROL biocides are either tethered to the coated surface or are released from the Surface into the Surrounding environment. CROSS-REFERENCE TO RELATED Use of these types of coatings has caused damage to the APPLICATIONS marine ecosystem, especially in shallow bays and harbors, 0001. This application is a continuation-in-part (CIP) where the biocides can accumulate. As such, the use of tribu application of U.S. patent application Ser. No. 11/567,103, tyltin has been banned in many parts of the world. These which is a continuation-in-part (CIP) application of U.S. products are effective for only approximately 2 to 5 years. patent application Ser. No. 1 1/202,532 entitled “SURFACE 0008 Foul release coatings present a hydrophobic, low TOPOGRAPHY FOR NON-TOXICBIOADHESION CON Surface energy, and resulting slippery Surface that minimizes TROL' which was filed on Aug. 12, 2005, now U.S. Pat. No. the adhesion of the biofouling organisms. The most com 7,143,709, which a CIP of U.S. patent application Ser. No. monly used and highly successful of these is a nontoxic 10/780,424 entitled “DYNAMICALLY MODIFIABLE silicone-based paint. The silicone-based coating requires sev POLYMER COATINGS AND DEVICES’ which was filed eral layers to make it effective, and therefore it can be quite on Feb. 17, 2004, now U.S. Pat. No. 7,117,807, each of which costly. Effectiveness lasts up to 5 years at which time recoat are incorporated by reference in their entirety into the present ing may become necessary. These products are considered to application. be more environmentally sound as compared to anti-fouling coatings because they do not leach toxins. However, they are STATEMENT REGARDING FEDERALLY subject to abrasion, and therefore their use is limited to areas SPONSORED RESEARCH ORDEVELOPMENT that are not Susceptible to damage caused by ice or debris. 0009 Biofouling is similarly a problem for surfaces used 0002 The United States Government has rights in this in biomedical applications. The accumulations of bacteria, invention pursuant to Office of Naval Research (ONR) Grant i.e. a biofilm, on implanted devices Such as orthopedic pros No. NOOO14-02-1-0325 theses present a significant risk of infection leading to com plications as severe as death. In cosmetic implants, devices FIELD OF THE INVENTION such as breast implants are fouled with fibroblasts and acel 0003. The invention relates to articles and related devices lular extracellular matrix resulting in a hard fibrous capsule and systems having Surface topography and/or surface elastic and Subsequent implant rupture. Blood contacting Surfaces properties for providing non-toxic bioadhesion control. Such as artificial heart Valves and artificial vascular grafts are fouled by proteins such as fibrinogen that initiate the coagu BACKGROUND lation cascade leading in part to heart attack and stroke. The accumulated affect of bio fouling on chronic and acute dis 0004 Biofouling is the unwanted accumulation of organic ease states, its contribution to morbidity and its massive medi and inorganic matter of biological origin on Surfaces. For cal expenses places biofouling as one of the major issues example, in the marine environment bio fouling is the result of marine organisms settling, attaching, and growing on Sub facing modern medicine. merged marine Surfaces. The bio fouling process is initiated SUMMARY OF THE INVENTION within minutes of a Surface being Submerged in a marine environment by the absorption of dissolved organic materials 0010. An article has a surface topography for resisting which result in the formation of a conditioning film. Once the bioadhesion of organisms and includes a base article having a conditioning film is deposited, bacteria (e.g. unicellular Surface. The chemical composition of the Surface comprises a algae) colonize the surface within hours of submersion. The polymer. The Surface has a topography comprising a pattern resulting biofilm produced from the colonization of the bac defined by a plurality of spaced apart features attached to or teria is referred to as microfouling or slime and can reach projected into the base article. The plurality of features each thicknesses on the order of 500 um. have at least one microscale dimension and at least one neigh 0005 Biofouling is estimated to cost the U.S. Navy alone boring feature having a substantially different geometry. An over $1 billion per yearby increasing the hydrodynamic drag average spacing between adjacent ones of the features is of naval vessels. This in turn decreases the range, speed, and between 10um and 100 um in at least a portion of the surface. maneuverability of naval vessels and increases the fuel con 0011 Surface topographies according to the invention sumption by up to 30-40%. Thus, biofouling weakens the resist bioadhesion as compared to the base article. As used national defense. Moreover, biofouling is also a major eco herein, a Surface that provides a Surface topography accord nomical burden on commercial shipping, recreational craft, ing to the invention can be applied to a surface as either a as well as civil structures, bridges, and power generating printed patterned, adhesive coating containing the topogra facilities. phy, or applied directly to the surface of the device through 0006 Any substrate in regular contact with water is likely micromolding. In the case of micromolding, the Surface to become fouled. No surface has been found that is com topography will be monolithically integrated with the under pletely resistant to fouling. Due to the vast variety of marine lying article. organisms that form biofilms, the development of a single 0012. The feature spacing distance as used herein refers to Surface coating with fixed Surface properties for the preven the distance between adjacent features. Moreover, as used tion biofilm formation for all relevant marine organisms is a herein, “microscale features’ includes micron size or smaller difficult if not impossible task. features, thus including microscale and nanoscale. 0007 Anti-fouling and foul-release coatings are two main 0013.