2) United States Patent Palumbo et al. US007S53553B2 US 7,553,553 B2 Jun, 30, 2009 (10) Patent No.: (45) Date of Patent: (54) ARTICLE COMPRISING 4 FINE-GRAINED. METALLIC MATERIAL AND A POLYMERIC MATERIAL (75) Inventors: Gino Palumbo, Toronto (CA); Jonathan MeCrea, Toronto (CA); Klaus ‘Tomuntschger, Mississauga (CA); Ta Brooks, Tomato (CA); Dachyun Jeong, Oakeille (CA); Dave Limoges, Etobicoke (CA); Konstantinos Panagiotopoulo, Toronto (CA): Uwe Erb, Toronto (CA); Andrew Wang, Toroato (CA) (TB) Assignee: Intogran Technologies, Inc, Toronto (cay (7) Notice: Subject aay disclaimer, de term ofthis pateat is extended or adjusted uader 35 USC 154(b) by 77 days (21) Appl.Nos 12/000,382 (22) Filed: Dee. 12,2007 ) Prior Publication Data {US 200810090066.A1 Apr 17, 2008 Related US. Application Data (G8) Continuation of application No. 1/300,579, fled on Dee. 15, 2005, now Pat. No. 7.354384, which is a continuation-in-part of application No. 110013456, filed on Dec. 17,2004, nave Pat. No. 7,387,578, (1) Intel B32B 1508 (2006 01) AGB 53/12 (2006.01) A63B 5310 (2006001) (2) US. 4281626; 4281413; 281458 “428/459, 4284461; 4281512 (58) Field of Classification Search. None ‘See application ile for complete search history. 66) References Cited US, PATENT DOCUMENTS 97.265. Lebowitet al 3516296 A, Beene al 3625039 A, Kubach tal 360.789 A, Hepter 3655453 A, Poppe eal. Been a Burgess 3806429 A, aves tal 3856613 A. Waller 3867.264 A, carson 949.988 A, Sister 397408 A 81976 Trem (Contin) FOREIGN PATENT DOCUMENTS OMLOB AL 11980 (Continued) Primary Examiner John J, Zimmerman Assistant Examsner—Aaron Austin (4) ttornes, Agent, or Firm—Bacon & Thomas, PLLC 6 ABSTRACT Lightweight articles comprising a polymeric material at east, parially coated witha fine-grained metallic material are dis closed. The fine-grained metallic material has an average ria size of 2m to 5,000nm, thickness between 25 micron and Sem, and a hardness bereen 200 VEIN and 3,000 VEN ‘The lightweight articles are stong and ductile and exhibit high coefficients of restitution and a high stiffness and are particularly suitable for a variety of application including aerospace and automotive pats, sporting goods, andthe ike 4 Claims, 7 Drawing SheetsUS 7,553,553 B2 Page 2 US. PATENT DOCUMENTS 6106417 A 82000 Lt G139.444 A 102000 Renata 4085519 A, Van Aken 6152504 A 112060 Dickson eta 4128208 Bums 68836 BI 1/2001 ‘Kukansis eta S193 A, “Tremmet 6179736 BI 12001 ‘Thar S1S8082 A Yanagioka 6198614 BI 22001, Sasamo a (218937 4 Albrecht ta 6334824 BI 12002 Filice ta 315045 A 2 Dilan al 6346052 Bi 22002 Chippll 431.750 A, Roy 6354960 BI 3.2002 Perryman ta. 4369.500 A, Papeahagen al 6403.168 B2 62002 Meyer tal 398,758 A, “Tabares 468672 B1 102002 Donan, Ita 44290020 A, Lich 6500.107 B2 12003. Ding etal 4533146 A, Schaar 6580320 B2 62000 Fendel 4552626 A LL98S. Stevenson 6645557 B2 11.2008 Joshi 4556607 A 121985 Sasi 66778 BL 12004 Hench ta AS98457 A TH9RS. Kink, 6692377 B2-22004 608168 A 81986 Lineal 6706326 BI 32004 4671852 A 69ST Anderon ea G7i2948 BI 32004 4906532 A 311990 Spencer. te 6729970 B2 $2004 Horwood w a, 4951953 81990 Kim {802.232 B2 102004 Buekley etal 4999227 A 34991. Vander Togt 6805642 B2 102001 Meyer SO1S339 A $1991. Peniton (684.716 B2 1/2005 Haein’ t a Sonam A 61991 Daly 860821 B2 3.2008 nose al 5028464 A 71991. Shigeoh (6860372 BL 32005 Higgnbotham etal G16} A 121991 Bauman 860.732 B2 42008. Takeuei eta 131985 A 74992 Harada a 690278 B2 62005 Marenoteet a S1g782 A 91999 Bengston 66915964 B2 72005 “Tapoen et al SUT8956 A 11999 Rychwalski tal 719.395 B Henin etl S302414 A 41904 AMHimoW ea 7318781 B Deshmukh A 611904 Hamat 2001/0051589 AL Inoue et A 61994 Zedan ao0200%4985 AL Pym ta A 61994 Minami 20020061374 AL O'Brien eal, A 101994 beta 20020082111 AL Hediok el 316.248 A 12/1904 Cond etal 200210008006 AL sa SH21989 A 61995 Stamp eta 2o020119829 AL Cheng SA33797 A 71908 Exbet al aoovn4ge2s AL Horwood a A 81998 Akaka etal 20040088675 AL Kuramot tal ‘A 1211995 Yamanaka o040092%29 AL Meyer A 11996 Schmid ca 20040002330 AL Maye ta A 61996 Pond doovor2i864 AL Momow el A 71986 Damerow eta 20040147346 AL Cassa, J 5538769 A 71996 Sandnan, J 2040244888 AL Hovimura at SS47S58 A 81996. Sakamoto et 200s 0003266 AL Smith ta SS7SISE A LL1996 Bauman oosioto3408 AL Kuehn ta SSOTAIL A L99T Ragpeet a ao0s 0.07182 AL Meyer tal S599.20 A 21997 Soluiche ta 20050124433 AL Sesugps ea S03667 A 21997 rahi tal do0st1103 AL Lind S6SS981 A RIB97 Reed 20060160636 AL 72006 Palumbo ct 565441 A 911997 Suave ea donoowsre2 AL £2006 Miura ta S666155 A LL1997 Suave eta DOUTODOSS48 AL 122007 Hocknal et a. 5713800. 21998 Su S7S5A26 A $1998 Beach a. FOREIGN PATENT DOCUMENTS, STII A 61908 Feroretal SBSIISE A 121998 Wintow al 2 stars A 10/1994 S881605 A 41999 Doolitle «a 2 3266967101997 5900.19 A $1999 Dishson eta 2 3285569 A 11997 5935018 A $1999 Tale 2 2o0o.61008 A 22000 S941329 A 81999 Iehioka ta WO WooHoaLIGO Al 1272003 5967904 A 101999 Naga eal WO Wo200H07H580 AL 92004 010,196 X 1.2000. Wang eta WO Wo2004002450 AL 10°2004 GOT6S02 A 62000 Maier WO WO2004004039 AI 11/2004US. Patent Jun, 30,2009 Sheet 1 of 7 US 7,553,553 B2US. Patent Jun. 30,2009 Sheet 2 of 7 US 7,553,553 B2 FIG. 2US 7,553,553 B2 Sheet 3 of 7 Jun, 30, 2009 US. Patent FIG, 3US 7,553,553 B2 Sheet 4 of 7 Jun, 30, 2009 US. Patent FIG. 4US. Patent Jun. 30,2009 Sheet S of 7 US 7,553,553 B2 Fixed Suppor ib 0.000__5.552 11.104 _16.857(in) FIG. 5US. Patent NODAL SOLUTION | STEPSt | sua im [usu (avg) | RSYS=0 | WX =24.626 | SMX =24,626 yy | | | z | | } 0 L Jun. 30,2009 Sheet 6 of 7 US 7,553,553 B2 eam sc ee 5.473 10.945 16.418 21.89 238 8.208 45.681 19.154 24.626 | eeUS. Patent Jun. 30,2009 Sheet 7 of 7 US 7,553,553 B2 FIG.7US 7,553,553 B2 1 ARTICLE COMPRISING A FINE-GRAINED. METALLIC MATERIAL AND A POLYMERIC MATERIAL CROSS-REFERENCE TO RELATED APPLICATION ‘Tis isa continuation of US. application Se. No, 11/300, ‘579, fled Dee. 15, 2005, which i a Continuation-in-Pant of US. application See. No” 11/013,456, filed Dec 17,2004, FIELD OF THE INVENTION ‘This invention relates to applying thick (+25 ym), fine tained (average grain size 2 nm to $.000 nm) metals, metal alloys ormetal matrix composites with high specific strength, toughness and resilience (20.25 MPs) to polymeric substrates. inorder achievea structral shell Antcles mde according tothe invention ind use ina variety of applications where the use of the high strength sizuctural shell oa polymer of ‘composite substrate allows for substantial weight savings. Applications include automotive components, aerospace pars, defense pars, consumer products, medical compeneats ‘and sporting goods. Suitable industrial pars include, among ‘thers, tubes orshafts use eg. sporting goods such as ski and hiking poles, shing ros, golf lub shafs, hockey sticks, Tacrosse sticks, haseballsftall bats, bicycle frames, skate blades, snow boards platos such as gof cub head faceplates; as well as complex shapes such as sports racquets (tenis, ‘racquetball squash an the ike}, golf elub heads, avlomtive arillguards; brake, gs or clutch pedals; fool als eunning boars: spoilers; mule tips, wheels, vehicle frames, struc tural brackets and the ike, Pars are at lest partially coated with said fine-grained metallic materials, ‘Theinventionalso relates to depositing fine-grained metal- lic materials dreely onto suitable substrates such as eylin- Arica, conical or tapered shafis. Alternatively, fine-grained ‘metallic plates or foils ad the like can be formes and subse~ ickel based alloys for the purpose of providing a wear resistant costing, The electroless aickelebating of ee is 20 um hick and the depsition ime is 20s, esuing ina cium silicate, silica, eleium carbonate, alumina, titanium oxide, ferrite, and mixed silicates. Minera-filled, plating rade polyamide resins containing powdered (e., 002-20, ‘mierons) mineral filers such as tale, calcium silicate, silica, calcium carbonate, alumina, tianium oxide, fete, and nixed silicates (eg, bentonite or pumice) having mineral contents of up to about forty percent by weigh and providing, high stength at relatively law cost are particularly suitable substrates. Suitable polyamides are available from a number ‘of vendor including Allied Chemical Firestone, DuPont and ‘Monsanto, 1 name a few. Other suitable substrates include acrylonitie-butadienestyrene (ABS) and. thermoplastic polyolefins (TPO), available in “plating grades” and option ally reinforced by variety of filles including plas fiber.US 7,553,553 B2 ul “The surface of the polymere pat as prepared by any sit- able molding oF forming operation is typically quite smooth andthe surface roughness Ra0.1 jum. To enhance the adhe siono the metalic coating the surface tobe coated is rough coed by any number of suitable means including, eg, ‘mechanical abrasion, plasma andl chemical etching o achieve ‘surface roughness in the range of Ra-0.25 um to Ra=25 un, The following isting describes suitable operating param- er ranges for practicing the invention: esis Lger Dk xi Stan.upt§ ca Msi Ate Gat ie Rane 1m, Msn ics VEN ‘30, 30400 sso aie VN) its 250 5000 Dente Rate ae: {ose ‘Yeu Sten Rane 20MPato 2750 Pe Minin Noda of Rese fe ase) MPs acre Met ayer 2p Sia Tee ationm Mes Reine of he 12s 25 Me lane Lin Rage oasiezars Pate Cote Rens 207% Sytehine Minima Sire Sure Rouges [Run] 025.04.05, anim State Sree Rohs sans asta ‘Thefine-grained metallic materials ofthe present invention cptionally contain at least 2.5% by volume particulate, pe erably a east 5% and up to 75% by volume particulate. The particulate can be selected from the group of metal powders, ‘metal alloy powders and metal oxide powders of Ag, Al,Co, Cu, In, Mg, Ni, Si, So, Pt, Ti, V; W ad Zn; nitrides OFA, B, Si and Ti; C (graphite carbon, carbon nanotubes, or ia- mond); carbides of B, Cr Bi, Si, Ti, W: MoS, ceramies, glass ‘and onganie materials such as PTFE and other polymeric ‘materials (PVC, PE, PP. ABS), The particulate average par- ticle size is typically below 10.000 (10 x), 5,00 am (S am), 1,000 nm (1 um), and more preferably below S00 nm. Te present invention provides for applying fine-grained metallic materials having a thickness of at least 0025 mum, preferably more than 0030 mm, more preferably more than (0.05 mum and even more preferably more tat 0.1 mato the surface of appropriate antics, Suitable ariles include sport- ing goods such as golf club heads, insets for gol lub heads, faceplates lor got clus: shals for golfelubs, hockey sticks, hiking and skiing pols, fishing poles, arrows ete. andanticles ‘withcomplex shapes suchas baseball bas skate blades, snow boards and tennis rackets. Suitable automotive articles include gilhpuards, brake, as or clutch pedals, fuel als, running boards, spiles, muller tips, wheels, vehicle frames, structural brackets. The fine-grained metalic materials ofthis invention have an average grain size under 5 ym (5,000 nm), preferably ‘under I (1,000 nm), preferably inthe range of 210750nm, more preferably between 10 and $00 nm and even more preferably between 15 nm and 300 nm. “Thefige-grained metalic material ofthis invention havea modulus of resilience oft last 0.25 MPa, preferably at eat | MPa, more preferably atleast” MPa, more preferably at least 5 MPa and even more preferably a east? MPa and up 1025 MPa, vo 8 s 12 ‘The fine-grained metallic materials ofthis invention have anclatc limit oft least bout 0.75%, and preferably greater than about 1.0%; and preferably greater than 1.5% an up t0 20%. ‘To ensue part reliability, iis preferable to maintain the average thickness to average gruia size ratio of the fine- rained metallic material layer at a minimum value of 10, preferably greater than 500, and more preferably greater than 1,000: and upto 1,250,000 and as much a 25,000,000. Ina prefered embodiment ofthe proces ofthis invention, dispersion sttegthening ofthe fine-grained metallic materi als is performed by a subsequent heat-treatmeat, ‘According to this invention, patches oF sections can be formed on selected area ofthe polymeric substrate, without the need 1 coat the eatire artile “According to this iaventon patches o sleeves of the fie- rained metalic materials are not necessarily uniform. in thickness and can be applied in order to eg. enable a thicker ‘deposit on selected setion or sections particularly prone to Ineavy use suc 2s golf club faceplates, the tip end of fishing poles snd shafs forgot clubs, king or hiking poles et. BRIEF DESCRIPTION OF THE DRAWINGS In order to better illustrate the iaveation by way of examples, descriptions are provided for suitable embodi- ‘meus of the method)processapparatus according to the invention in which: FIG. 1is a picture of a ewss-sectional view of a m-Ni coating appli io a graphitelepoxy hybrid golf shat. FIG. 2isa picture ofa polymer amaunition casing (0.233 caliber) that has been reinforced by a layer of fine rained [Ni20Fe, afer firing. FIG, 3isanimageofa Smm thick n-Ni—Prepoxy laminate produced to form thick (5 mm) laminated assemblies. FIG. disa picture of an-Ni-lOFe adhesive tape applied to «tubular automotive part FIG, Sshows plastic grille-guard fora tack containing 3 fine-grained metalic coating 1 add stifiess. (6 mm plastic ‘with 0.01" n-Ni20Fe coating) FIG. 6 shows the deflection of the plastic gril-uad con- taining a fine-grained metallic coating with a 280 Tp load applied atthe eross beam, (Faget dellection: <25 mm; Per- formance 24.6 ma FIG. 7 shows scctions of nanocoated-PC/ABS (left) and stainless steel cight) automotive running board parts. ‘The present invention is intended for depositing fine- grained metallie materials ont ates nthe form of external or internal coatings or eletroforming fine-grained metallic ‘materials comprising a metal or alloy selected from Cu, Co, Cr, Ni, Fe, Sa, Mo and Zn optionally with particulate dis persed in the fine-grained layer and subsequently applying the fine-grained metallic materials to the substrate. DETAILED DESCRIPTION OF PREFERRED EMBODIMENT This invention eles on producing fine-grained, coatings by suitable metal deposition processes including DC or pulse @ electrodepostion. ‘The person skilled in the at of plating, in conjunction eg. with US. Pat. No. 5,352,266 (1994), US. Pat, No. 5,433,797 (1995) andin DE 10,288,325 (2005) [-US. Ser. No, 10/516, '300(2002) and WO2004/001 100.1 2002 cited already. will, ‘know how to electrodepsit selected fine-grained metals or alloys by selecting suitable plating bath fomnulatons and plating conditions. These patents ar incorporated herein byUS 7,553,553 B2 13 reference for their disclosure of electrodeposition methods Optionally, solid particles can he suspend inthe electrolyte ‘and are included ia the deposit as described ia DE 10,288,323 (2008). The person skilled inthe art of PVD, CVD and cod spr {ng willalso know how to deposit selected fine-grained metal- lic layers on suitable substrates. ‘Minimizing the weight of articles, which is desirable for ‘numerous applications, can be achieved by increasing the strength of the metalic materials by grain-size reduction. 10 Depending on the ductility required, the grain size of eg. [Nicbasd coatings in the range of 2m fo 5,000 nm, prefer: ably 10 nm 500 nm provide suitable mechanical properties. epening on th requirements of the particule spplica- tion, the material properties canalso be altered, eg. by incor. porating dy lubricants suchas MoS, and PTFE), abrasion or ‘wear resistant particles, Incorporating a suficient volume fraction of particulate can therefore be used to further chance the material properties. Generally, the particulates «ean be selected from the group of metal powders, metal alloy powders and metal oxide powders of Al, Co, Cu, In, Mg, Ni, Si, Sn and Zn; nitrides of Al, B, Si and Ti; C (graphite, diamond, nanotubes, andlor Buckminster Fullerenes) cat- bides of B, Si, Ti, Ws self lubricating materials such as MoS., ‘organic material such as PTFE and polyinerie materials ‘As noted above, particularly sited applications forthe fine-grained moalic materials disclosed herein inclu gol shall ski poles, fishing rods, hockey sticks, tennis racquets, bicycle frames and other articles and structures comprised of conventional metal, polymer or graphite composites that are coated on at east pat ofthe interior andor exterior surfaces, or altematively are net-shape formed with the use ofa tem- porary substrate and subsequently applied to the permanent substrate. Conventional metals eg. aluminum, copper, nickel and their alloys are relatively soft, permanently deform and break easly asa result of the bending and torsional loads encountered during use. Furthermore, these materials with conventional grain-sizes above 10 um, generally exhibit alow resistance to abrasion and cut or scratch easily andcan benoit from the fine-grained metallic layer described in this inven- tion, Shalis made from composites of syathetic resins and filaments are more resilient under bending forces than alumi ‘oum, but lack sufficient strength. Ths deficiency, however, can he overcome by applying a fine-grained metallic layer according tothe present invention. ‘The rebound distance of an object, eg. a got ball, tenis ball, baseball or the lke when it impacts a certain material is a funetion of the modulus of resilience, U,,of the material, Which is expressed as: (Goals Handbook, Nath Eiion, Volume 8, Mechasial “Testing, American Society for Metals, Materials Park, Ohio, 44073) ‘Where; isthe maximum restrain at the yield pint, 0, represent the yield tenth and E the modulus of esti. ‘As ine-prined mates deseribad in this invention possess yield strength valves, which arethreeto five and up o ten Times aester hat those of conventional coarse-grained met- als, the sence (rebound distance capacity) can hereore boners nine to went ved and upto re fl. ‘Themodulusof els E, however, isypically not aleted by nolucing the arain size of a given metic mistrial, pro s 4 vided the material is flly dense. The modulus of elasticity, however, can be altered eg. by using metal matrix compos= ites, Material properties required fora numberof applications also ince a high elastic stran-to-faiture limit, Low damp- ing characteristics (ow absorption and high release of energy) ensure that even ae high load and siress deforma ‘tion the material springs back wits orginal shape as required fn sce faces, eg. i selected automotive applications or sporting goods such as poled faceplates and baseball bats Conventional metals have elastic stain limits of 0.65% oF less. The curent invention is dzected to metalic mateils. having elastic limits of at least about 0.75%, preferably rear than about 1.0%; and preferably greater than 1.5% and up 102.0%. FIG, 1 is a picture of @ cross-sectional view of a a-Ni coating aplied to praphitetepoxy golf shat, Carbon fiber ‘composites possess much higher specife iidity and lower density than steel; however the light-weight, carbon-fber golf exhibits undesirable twisting othe club head relative to the shaft on down-swing and particularly at ball contact, resulting in por accuracy and lying distance. This limitation can be overcome by coating at lest 10% of the composite shaf's external and/or intemal surface with the fine-grained metallic ayer described FIG. 2isapietureofa polymerammunitions earidge with a base that has been reinforced by a layer of fine-grained 1Ni-20Fe, The fine-grained metallic material layer provides high steagth and a low coeficent of friction. FIG. 3 isan image ofa $ mm thick a-Ni—Prepoxy resin laminate produced to form thick (oS mm) laminated assem- biies according to one prefered embodiment FIG. disa pious ofann-Ni-10Fe adhesive tape applied to tubular automotive part. As will be described in greater etal below this fine-grained metallic layerean be applied as an adhesive tape to at lest pat of polymer article. FIG. § shows. plastie gril guard fora track containing fine-grained metalli coating (n-Ni-20Fe) to ad sifiness ‘This partis blow-molded in PC/ABS and with plastic alone, doesnot moot the dellection and vibration requirements for ‘theapplicaton. The performance requirements can be met by adding te tf, ightweight fine-grained metalic costing FIG. 6 shaws the deflection encountered hy the plastic aill-guand containing the fine-grained metallic coating with 2501bf applied atthe erss-beam toe 24.6 mm which meets the requirement of a maximum deflection of 25 mim. FIG.7 shows sections of nanocoated-PC/ABS and stain- less see automotive running board parts ‘Various non-metallic materials ae now commonly usedia the manufseture of sporting goods, automotive components, aerospace pars or industrial articles and include polymeric resin malrix composites employing materials including ear- bon fibers, ceramic mati, aramid fibers, polyethylene fibers, boron, fiberglass, and various thermoplastics ineluding, but sot limited to, polypropylene. polyethylene, polystyrene, vinyls, aerylies, nylon and polyearbonates, among oer As highlighted numberof processes ean be used 0 apply the fine-grained metallic material to the polymer substrates. Inthe case of PVD, CVD, cold spraying or the application of ‘an aesive fine-grained metal tape, the sufice of the sub- strate may not require any preeatment. If eleceoplatiag is used to apply the fine-grained moalic material a good bond. canbe achieved when suitably roughening the surface ofthe substrate, Non-conduetive polymer substrates can be ren ered suitable for electroplating by applying a thin layer of a ‘conductive material eg, by electroless deposition, physical or chemical vapor deposition, or applying electrically conduc-US 7,553, 15 tive paints by various means. It should beclearto those skilled ‘nthe art thatthe subject invention encompasses the use of virally any substate material According toa further preferred embodiment ofthe present invention, its also possible to produce fine-pained coatings by electroplating without the need to enclose the area of the ariele wo Be coated and frm a plating bath around it, Selec tive brush or tampon plating is suitable alteratve, particu larly whea only a small portion of the workpiece isto be plated. The brush plating anparatus wypically employs a 0um ‘ofc ged BON 20Fe and Ss Nyon a rot ‘ile ied IN: 20 ant 984 ABS Compote ‘inn 358.76 gine ho 36 iin >10 a) 104) gle, gs einoed sain Nel gan soe Onn) a ow ms as an ar) 429 noo so w 186 o Example 2 1-Ni Costed Graphite Epoxy Golf Shaft—25% Ni Peake arophite epoxy Light LS S-Fex and Penley™ -85X- Flex graphite epoxy shalls were used. The S-Flex shaliswere characterized, stnppd of he sn. Thesuraceot te shafts was mechanically abraded using snd blasting toa surface eovghness of Ra-2.1 yun and subseguenty plated ‘ith coarse and fine-grained coatings. Pate -Flex shafts and unplated X Plex shafts having otal overall weight o89 2 Were perfomance ested The Nisleeves were apple o he outside ofthe S-Flex graphite golf lb shafts (OD, 0.586", tapering down to OD,-0.368" over a length of 405°) by clecteleposton in a modified Wats nickel bath and using a vo 8 18 ynatronix (Dynanet PDPR 20-30-100; www dynatronix. com) pulse power supply. The starting mass of each S-Flex shafl was 7.5 gand prior electroplating approximately 6.0, ‘2 of paint was stripped of. The coating procedure comprised three steps, namely (1) a thin electroless nickel plating to chance the electical conductivity using a procedure and chemicals povided by MacDemnid Industral Products (w= ‘wanacixustrialprodvcts com) to achieve an average metal film thickness of 0.4 micron at a deposition rate of 17 wavhe and (2) electroplating 10 form the fine-grained or course- ‘trained coating by varying the duty cycle and he peakcurret density. The electrolyte composition was 300 nickel sul- fate, 45 gl nickel chloride, 45 wl boric acd (11,B0,),2 gt saccharin and 3 mil NPS-91. Standard levers and bright- ‘ners were employed and Inco nickel “R-ouads Were used. fas anode material, The weight of the metal coating was approximately 20g, The electroplating conditions and metal- lic layer properties used are summarized ia Table 3. FIG. 1 provides a picture of a eross-sectional view of the n-Ni coat ing applied toa graphitelepoxy golf shat. TABLES “Hest oni Fine Goae ate! Ora ‘Depstion epee (C] @ @ Dat OrlePs) 8 ry Den a ate 5 ts gene Thetis ja] 3S * ‘eng Gain Si) bos YikdSieagh (a) 9 26 ars [EN] 0 0 Flexural stiffness was measured with a GolfSmith™ Fre quency Analyzer and the frequency was comverted 0 a FlexRating (sill, X-extra sti). The torque values were determined using a GolfSmith™ Torque Arm with 1 16 torque 2” fom the tip end ofthe shaft, The data are summa- ‘ized Table 4and indicate that significant improvement ia the torque values canbe obtined by replacing some fraction ofthe original weight of a graphite shat with an electrode posited costing, while maintaining the overall otal weight. Professional yolfers also teste these gol clubs. The eel bockreceived suggested tha the clubs made according to this invention exhibited a superior feel when compated to con- ventional graphite or steel shafts. Furthermore, the fine~ tained costed graphite shafls performed unlike either con- ‘ventional graphite or steel shafs. Compared to graphite the ball uajectory was reported to more coasisent, as expected from te significantly improved torque value measurements ABLE 4 ‘Soomarinna Gol Sh Pores, Gupkie Fine Coase sie ‘Shit _Gninol Grint CGnphae Sak Wegh Belew —=wBS TLE TL Cosh Delton Ref Coating x os 8 “are ale Cong oe aug weit (a, Na 2 200 Taleo BS ONS is ‘Tague Aer Cotig eeeUS 7,553,553 B2 19 Similar performance benefits are achieved when he coated anicles were fishing ods, hockey sticks, baseball als, tennis racquets, bicycle frames and the like as well as automotive, aerospace and other industrial components Example 3 Ni Coated Graphite Epoxy Golf Shaft—$-90% Ni Example 2 illustrates the benefit of relatively thi, fine- 10 grained metalic coatings with a thickness of >25 um and a Fine-grained metal content of about 22% of the total weight ‘To investigate the effet of futher increasing metal content, haybrid graphite epoxy/metl golf shafis were prepared and cbaroctrized. True Temper Prolaunch®™ (A-Flex) driver ‘uaphite epoxy shafts were mechanically abraded using Scotch-Brite to an average surface roughness of Ra-1.7 um and subsequently coated with fine-grained metallic nickel layers of varying weighs. The process and the characteriza tion techniques employed are described in Example 2, Table 5 shows the torsional stillness at a function of the meal content of graphite/metal composite golf shats, ‘The data reveal thatthe torsional stifles per uit weight ofthe article containing a metalic coating representing 5% of the total ‘weight i improved by atleast about St when compared to 2 the torsional stillness ofthe same article nt containing the ‘metallic coating Further improvements in the torsional silf- ress are obtained when the relative metal content of the haybrd shafts frther increased at arateof appeoximatelyone percent improvement in torsional siTness per percent rela tive metal content. “The torque and defletion data indicate that a significant performance improvement can be obiined by increasing the ‘relative metal weight of the composite graphite epaxy/metal shafls. Graphite!metal compesite gol shafts incorporating a ‘metallic coating representing atleast 5%, preferably more than 108% and even more preferably more than 20% ofthe total weigh provide a substantial iiprovement over the per- formance of uncoated graphite shafts Similar performance benefis were achieved when the coated anicles were fshingrods, hockey sticks, baseball ats, Lacrosse sticks, tennis racquets, biycle frames andthe ikea well as automotive, aerospace snd other industrial pars x“ TABLES G uve Changes Ton Met Coste fight Shah Sif per Une Weigh (eight 94 NaF] perdegreikg) “ 3 3 5 3 Bxample 4 a row Shafi NiFe on GraphiteEpoxy—Brash Plating (Over time a numberof articles inching archery arrows, baseball bts, hockey and Lacrosse stick, bowling pins pro grossed from being made out of Wood ta aluminum. Spec s 20 cally to €g, amows, aluminum arows are about 25% lighter than cedar wood arrows but with repeated use aluminum. mows tendo bend causing inconsistent trajectories and hss in accuracy. More recently. graphite composite artows appeared, made from carbon fiberspolyvigl or polyester resins, Graphite composite arrows are lighter an tougher than slumium and they do not bend when striking hard objet. The lighter weightalso lads to increased sped resit- {ng in delivering higher kinetic energy’ on impacting the tar- se. Sateo thea graphite eomposite arms, however, also hhavea numberof imitations. They tend to oseillate along the shu, which causes inaccuracies in ight and reduced pen- tration afer hing game. Due to the raivly limited “spine weight” and their low stiffness, it is dificlt to use ‘bem with Bows with more than $0 Tb draw weight. Purher- ‘more, upon penetrating the target the lietion generated heats up the tp section ofthe shaft oa temperature of over 150+ 200°C, which is significantly above the maximum tempera- ture the grophit ferepoxy resin composite i able to with- stand, resulting in degradation of the graphite fiberiepoxy resin composite shaf, deterioration of its performance and ‘imately fre ofthe sha ‘To demonstrate the performance of composites made of fine-grained metallic materials with polymers selected 30" mows were used including 4" outer diameter sraphite-2p- onyifiberlass arows and Ye" outer diameter Alumina cored srapite-eponyfiberlass arrows. To improve the shat performance and reduce the impact damage the test shafts ‘were reinforced with an outer layer thickness: 4 mils) of fine-grained Ni-20Fe alloy around the tip section after mechanically abrating the surtace to be plated with Scorch Brite to an average surface roughness of Ra-O 6 ym. The reinforcement layers extended par ofthe way (eg. 4") o all. the way up the length of the base shat making the shat more resistant to impacts an thus inereasing its drab The brosh plating procedure described in U.S. Ser. No. 10/516,300 was flowed for coating arow shafts with fine- asad Ni-20Fe with an averoge grain size of 20 nm wsing selective plating unit supplied by Sifeo Selective Plating (wwwbrusiplaingcom). A DC. power supply was employed. Standard subsrate cleaning and activation proce- dures provided by ifeo Selective Plating were used. Afterthe portion ofthe shaft be plated ws abraded and metalized by silver spraying, a fine-grained Ni-20Fe layer was pated onto the outside casing from the baseto between about balf'o the entre overall length by mounting the sha in rotator ‘wich also provide forthe electrical contact tothe metal- lized layer graphite anode brush wrapped in suitable absorber was brought into contact withthe rotating araw 10 deposit the fine-grained! Ni-20Fe layer (averaae grain size 20 1m). The eleewolyte was & modified Watt's bath foe nickel. containing 300 g/ nickel slate 45 pl ickel chloride 45 gil boric acid (HB0;), 2 saccharin and 3 mil NPA-O1, To form the desired n-Ni20Fe alloy 12 a FeCl, 0, 81 gl FeSO, 7H,0 and gl Na-Citrate were added to the modified ‘itis, Standard levelers and brighteners were employed ‘The -Ni20Fe was deposited using DC (100% duty eye at. current density of 100 mAVem® and 6 C. Test samples wer prepared with the fine-grained Ni20Fe coating representing between Sand 50% ofthe total arrow ‘weigh. The haf were ite with field tips, nek and sit. able vanes and submited to tests using a compound bo with a draw weight of 60 Ib, Overall the amows containing the fine-grained metallic coating consistently outperformed the coated arrows, Samples witha fine-rained metal layer of at least 5% of the total weight of the aow displayed a performance superior to that of conventional graphite fiber!US 7,553, a epoxy and aluminum arrow shafts. Reinforeng the arrow shaft in the tp section (2° to 8") with a 0.001"-0.008" thick ‘fine-grained coating proved particularly beneficial. Example S s Polymer Ammunition Casings; NiFe on Glass-Filled Nylon Ammusition containing plastic components including polymer cartidge casings are kaowabuttodatebavenot been produced economically in commercial quantities with ‘acceptable safety and consistent ballistic characteristics, Lightweight, polymer-cased ammunition utilizing standard projectiles, primers, and propellants have the potential t0 significantly educe the weight of ammunition, Deficiencies encountered to date include: the possibility exists that the projectile ean be pushed into the cartridge casing or fall ut: ‘moisture uptake and sang problems can occur filing to keep the propellant dy ‘ poor fit ia the chamber can cause problems with incon- ‘stat projectile accuracy de to the variation ia the as pressure during firings during the residence time ofthe caatrige inthe weapon > (affer chambering and before firing) the cartridges can be exposed fr some time o high temperatures of up to 200 oF even 300° C., eg, in automatic weapons which an degrade the polymer. ‘when fired plastic casings can pormanently deform or ro Vide insuicient elastic spring back causing dificulies during extraction; portions ofthe polymer eartridge casing can break off or lisategrate upon fring problems can be encountered with ease ad eliabibty of spent polymer cartridge extraction reqiting a metal base ofa metal inser: {jamming in automate weapons can occur particularly dar ing ejection ofthe casings insulfcient lubricity of the casing fils to ensure reliable extroction and jection; and ‘excessive cost ca be incurred due to complex designs and ‘manfactring processes required, ‘To demonstrate the performance of composites made of fine-grained metallic materials with polymers 61mm (0.223 4s caliber) polymer ammunition casings made of ZytelR,atype 66 polyamide containing 40% glass filler, were sedand were reinforced with a fine-grained metallic layer. Prior to plating, the outside diameter ofthe casing obe plated was reduced to accommodate 0.001" to 0.010" thick coatings without chang ing the outer diameter. The average surlace roughness was determined to he Ra~O5 un, No adjustments were made to the inner diameter ofthe casing in ease the inside surface was plated. The electrolyte deseribed in Example 4 vas used for coatingallthepolymerammunition casings with fine-grained 1Ni-20Fe with an average grin size of 20 um. Inco Ni “R™ rounds and electrolytic ion chips were used as anode mate rial in typical tank plating setup. The portion of the easing ‘ot to be plated was masked off and the area to be plated metallizad by silver spaying. The casing was mounted in suitable holder and submersed iato the plating tank, The fine-grained Ni-20Fe layer was plated onto the outside easing fromthebaseto betwoen about halftothe entre overall length whilethe casing wos oat inthe tanking DC 100% ty cycle) at a current density of 100 mAVem™ at 60° C. Test 6 ampes were prepared with the fine rained Ni-20Fe coating representing between S und 50% ofthe foal casing Weight 8 553 B2 2 ‘Thecasings were fited with primers suitable powder charges, ‘and 35 grin FMI projectiles and submited to test firing in an [M-16 weapon. The performance ofthe cartridges with respect to chambering, eectng and aecuraey was monitored Spent casings were examined with respect to their mechanical integrity and signs of disintegration/racking. Cracks and signs of polymer disintegration were observed frequently in the uncoated casings. Depending oa the coating thickness ‘sed, cracks and disintegration ofthe polymer was observed (Cracks inthe fine-grained coating were at times noted, to, ‘pica initiated inthe extractor groove, where the cating Was the thinnest. Overall, the easings containing the fine rained metalic coating consistently outperformed the ‘uncoated casings Samples witha fine-grained metal layer of at least $9 of the total weight of the casing displayed a performance equivalent o that of conventional bass casings. ‘The overall weight of the casings containing fine-grained coatings displaying, acceptable overall performance was reduced hy betvaen 10 and 75% when compared to brass cartidges. Benefits in reliability and performance of the ‘metal-polymer hybrid casings were observe irespective of ‘whether the casing was coated on the outer surface the inner surface o both, Reinforcing the easing acu the base as illus trated in the sample shown in FIG. 2 proved particularly beneficial Example 6 Ni Coated ABS5.90% NiFe Suitable materials for use in golf heads include thermo- plastic elastomers including styrene co-polymers, co-polyes- fers, polyurethanes, polyamides, olefins and voleanates. Suit- able thermoset polymers include epoxides, polyimides and polyester resins, In this experiment 2 | mm thick faceplate ‘made ofa platable ABS chemically etched using a suluric~ acidichromie-acid solution. The average surface roughness ‘was determined to be Ra-0.45 wm. After metalizing using the chemical Ag-spray the coupons wer lating using a con- ventional tank electroplating cell setup and employing the ‘Watts bath as described in Example 2 to deposit a 04 mm thick layer of fae-grained nickel on one surface. The nickel- layer surface was polished to a “miror finish” ultimately using 1 um diamond paste. A sample containing a 04 ma thick layer of conventional coarse-grined nickel was pre- pared a described in Example 2. The two samples were stitably mounted ona horizontal plate anda steel ball (3 mm. ameter) was dropped from a height of 60 em onto the samples. The rebound height was determined to be 2.9 mm forthe conventional nickel layer, while the rebound height of the fine-grained nickel sample was detemniaed tobe 28.8 an, ‘The rebound height off the fine-grained Ni-smple improved bya factor of approximately 10, as expected based on the 10 fold improvement in resilience (Table 6), TABLES soli Contos, This tention Por (linea) sane ped) renee Coning Tckoe fics) ry ‘ere Gras Sa “2s ” RaioCasingThkeeeGnin Sie 16900 » Depo te a] ‘s ik Datyeyse 4) s 1 Degen Tepes.) w oUS 7,553, 23 ‘TABLE 6-continued pang Coins Thitnemion eA (Gear) four gies) ‘Ye Sten [MPs] om 76 Ress, MPa us on 0 ‘Reound eile} 28 2» Inpovenem inRetows Hei) ° Example 7 ‘-Co—Ti02 Faceplates MMC on Polyurethane A nanocrystalline Co—TiO, nanocomposite of 0.12 mm average coating thickness was deposited onto a number of polyurethane golf head faceplates oma mealfed Watts bath for cobalt using a soluble anode made of electrolytic cobalt pieses and a Dynstronix (Dynanet PDPR 20-30-100) pulse 2 power supply The electrolyte used comprised 300 gl cobalt. sulfite, 45 gl cobalt chloride, 45 g/ boric acid, 2p saccharin and 4 mill NPA-91. Suspended in the bath were 0-500 g/l titania particles (<1 jm particle size) with the id of 012 gi [iklad™ particle dispersant (McDermid Ine.). The eectro- plating conditions and metalic layer properties used are sum ‘marized in Table 7, Prior to electroplating the polyurethane substrate surface was mechanically abraded using Seotch- rite wo an average surface roughaess of Ra-1.5 ys fal- lowed by metallizing using commercial silver spaying, A series of coated samples was produced using the modi fied Watts bath with the addition of TO, panicles (particle size <1 jm) ranging from 50 a 0 500 g/l. Table 8 ilusrates 8 the popes ofthe deposits ° TABLET, Eesplang onion . Dep prone PC @ Day eye ss Deen Rae jt) * ‘es Conn These] a ‘wens Gain Si i) tons uo Caine Tiss Sine 00 5 BLES CTO, Mel as Como Pps. s aio, Sie TO, ‘Cm Digest fo Fn Mi certian Consent inept tare samle “el ta “Tonk ohmnes) MNT gy unio ry ee cea oes ase 5 om 3 7 oR ssn 8 6 oo ow 6 553 B2 4 Example 8 ‘-NiP FacepltesBrush Plate, HT Prepare Laminate Gluing Together with Adhesive 10410 cm wide, $0 hick sameryslline N-0.6P fils (average grin size: 13m, 780VHN) were deposited ont a polished Ti cathode immersed in a meted Wats bath for nickel as describe in U.S. Ser.No. 10516300 (-WO20) 001100). soluble anode of Ni rounds contined in ta ium wite basket was used. The ellosing plating conditions ‘were employed Average current density: 150 mien Day Cycle: 100% Deposition Rate: 0.075 mavhe Electrolyte temperature: 65°C "eewust cvlation ate 0.15 liter per min and en* ea ode area The electrolyte used comprised 137 pl nickel slate, 36 nickel carbonate, / phosphorous acd and 2 soca Fa. The cecieoplating conditions and metallic layer proper ties used are summarized Table9, The fine grained N-0.6P frils wore sobsoquentlyheat-teaed as indicated to fue chance the mechanical properties by precipitation harden- ing ‘\ aminate part was prepared by stacking an joining 10 Ieabteted N-O.6P fi samples estas at 400° C ‘sing an epony resin adhesive (3M™ Scoich-Weld™ Epoxy “Adhzsve 1838 BIA: www3m.com) FIG. 3 shows 2 cos Seetional view ofthe laninat. The laminae was eu 1 ize foruseasa fice pla inser on a gol hb ead TABLES tmp Conus Depeton Tepes) s buy cys Pa uo Dapein Rae a] 0 eng Cosig The: on) 50 sverige ri So) ‘ats io Cea Tikes Ga Sze sas ares (VEN) "a0 (ar 20m [VEN] nde ee Tenet (ar Ct pon 20°C hs) VEN mo Alteratvely, fine-grained metal and metaalloy fils can be prepared by CVD or PVD, 0. using reo-to-rel system, Similarly, cold spraying as described in U.S. Pat. No. 5,302, 414canbe used toe g. prepare fine-grained metal and metal~ alloy layers Example 9 _NiFe Tape on Graphite poxy Resin Mountain Bike Frame Tube Using a drumplter nanoerystalline Ni-2SRe alloy foils (average grain size 15 am, Hardness: 750 Vickers) were 0mm «Ste ——«SD ke POABS+Stclbncite mm Mmm MOUS Ser BC ABS Son 3mm tie Ta Ser POABS wa Som 26mm = WSHe ADE Example 11 requirements for this automotive application namely a deflec- tion of less than 1" with a 250 Ib force applied and a first natural frequency of above 30 Hz. Upon analysis, stiffening by increasing te plastic thickness required to stiffen the part ‘went beyond the limitations of the blow molding process ‘used, To mee the silness requirements, formed ste! brack- «etsserewed onto the backplate could be used bt increases the cost and weight ofthe grille guard A0.001" (0.025 um) thick lightweight, fine-grained Ni-20Fe coating was applied to reinforce the pat aftr abrading the surface to becoated to an average surface roughness of Ra-0.6 um, The addition ofthe fine-grained metal layer to the polymer part substantially increased the stiffness of the part and met the defection and frequency performance required. The fine-grained Ni-20Fe coating only added 153 grams of weight to the part keeping itbelow the target weight of 50 Ibs. FIG. 6 shows the deflac- tion of grille guard containing fine-grained metallic coating ‘ith 250IbFapplied atthe cross beam. The maximum deflec~ ‘ion tolerated is 1" (25 mm) and the deflection encountered ‘with the par as illustrated is 246 mum, Similarly, with respect. to the natural frequency the grille guard conning a fine- arained metallic coating displayed a frequency of 30.3 Hz ‘which met the requirement ofthe target frequency of over 30 Te, s -NiFe Coated ABS Running Board ‘To demonstrate the henefis of polymer parts reinforced ‘with # nanostructured material, commercial stainless stel aulomotive runing boards were sourced, Standanl 3.5" OD PCIABS tubes were also obtained for plating to achieve a structural shell with similar stiffness fo the ste) euning board. After suitable activation (initially the substrate surface ‘was roughened with Scotch-Brite to enhance coating adhe sion; ech tube was metalized using silver spray followed. by a Cu pre-plte to reader it conductive enough for subse- quent electrodeposition of the fine-grained material. The entire outer surface was coated with a layer of n-Ni-20Fe (average grain size 20 nm) as described in Example 5 to a thickness of 0000". The average surface roughness Was var fed between Ra-05 pm and Re-15.0 wm by changing the abrasive media accordingly. After the application ofthe fine= ‘rane coating, the surface roughness decreased to between about 1s and o the original value due tothe leveling effet ofthe electrodeposited layer, Sections of the original metal running board and nanocoated PC/ABS runing boards are showin FIG. 7.US 7,553,553 B2 27 ‘Table 12 indicates tata 3.5" diameter PCIABS tube with 10.009" coating of -Ni20Fe (average grin size 20 am) enhances the sifhes of the polymer part tobe equivalent to the steel part yet yield a 43% weight savings. ABLE 12 Rew of Sui Anais fr Nano Rune Ba Pesan JO4Suinss oglsw —_CIABS Sette Shel fll 30% ae Fi ‘inate Bera 30 35 3s “hss ‘ins oa ois ess [] s a 1 (Nea) Ebsieer 8:2 soot a est ol ey Ms 10 2 Fae Grud Caing NA pnidire ‘Ths = = oe Desi (et) = = ts Mode East = 18 (st Exsiess[N- a 439 Mas] = = uN FantedPodae 06S CABS CARS ‘Sel Sal 386 Gla Fl ‘a ‘ere sisi [8a s aa S20 Mas kl 2 Ib 333 ‘Nei Sng ve s MASS Bl ‘The nanostructured coatings passed standard peel tests, although it was observed thatthe coating adhesion improved significantly with ineweasing the surface roughness of the substrate before plating. Specifically a surface roughness of the substrate in the Ra-0.25 im to Ra-S.0 ym range proved particularly beneficial while not compromising the appeat- ‘ance, Selected parts were exposed toa variety of mechanical tests, The results indicated that hybrid nanostructured metal 28 polymer running boards provided adequate durability and Performance while reducing the weight by 40-50% wen ‘compared with, eg. stel runing boards Similar performance benefits are achieved when substrates 5 including carboniepoxy, PTOs, polyamide, polypropylene ‘and wood were coated using the same approach. Variations “The foregoing deseription of the invention has been pre- sented describing certain operable and prefered embod ‘mens. 1 is aot intended that the invention should be so Timited since variations and modifications thereof will be ‘obvious to those skilled in thea al of which are within the spirit and seope of the invention, ‘Wha is claimed is 1. Anarticle comprising: (@)a permanent substate comprising a polymer material with or without particulate addition, and ) a fine grained metalic Iyer having 2 gran size inthe range of 2 10 5,000 nm, a thickness ranging fom 30 ricrons © 5 em, a modulus of resilience ranging from (0.25 o 25 MPa; and ‘wherein a surface of sid polymer substrate is costed over at least a portion thereof with the fine grained metallic layer or an intemeiate conductive layer whieh is coated with said Fine rained metalic layer and hasan average surface rough- nessof 0.2510 25 micron over at east the portion whichis coated. 2, An article aoording to claim 1, wherein said article contains a layer intermediate () and (i selected from the aroup of a metalic intermediate layer, a polymeric adhesive intermediate layer and a conductive polymere intermediate layer containing conductive particulates '3. The ale of claim 1 which has a yield strength of at leas 25 MPaanda bending stiliaess peruait weight improved 35 by a east 58% compared otha of the same article without a fine grained metallic layer and an intermediate layer. 4. The article of claim 3 whichis a mold. w