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Title:
ADDITIVE PROCESSING OF FLUOROELASTOMERS
Document Type and Number:
WIPO Patent Application WO/2017/127569
Kind Code:
A1
Abstract:
Provided are method of producing a shaped fluoroelastomer articles. The methods include subjecting a composition comprising a fluoroelastomer to additive processing in an additive processing device. Also provided are articles obtained with the methods and 3D-printable compositions.

Inventors:
JIANG, Xuan (3M Center, Post Office Box 33427Saint Paul, Minnesota, 55133-3427, US)
BARTOW, Jeffrey N. (3M Center, Post Office Box 33427Saint Paul, Minnesota, 55133-3427, US)
ARREN, Dirk H.C. (Hermeslaan 7, 1831 Diegem, Diegem, BE)
ZENTIS, Fee (Carl-Schurz-Strasse 1, Neuss, Neuss, DE)
HINTZER, Klaus (Carl-Schurz-Strasse 1, Neuss, Neuss, DE)
GOTTSCHALK-GAUDIG, Gabriele H. (Carl-Schurz-Strasse 1, Neuss, Neuss, DE)
Application Number:
US2017/014174
Publication Date:
July 27, 2017
Filing Date:
January 19, 2017
Export Citation:
Click for automatic bibliography generation   Help
Assignee:
3M INNOVATIVE PROPERTIES COMPANY (3M Center, Post Office Box 33427Saint Paul, Minnesota, 55133-3427, US)
International Classes:
C08F259/08; B33Y10/00; B33Y30/00; B33Y80/00; C08L23/12; C08L27/18
Domestic Patent References:
WO2004113042A22004-12-29
WO2000009603A12000-02-24
WO2007133912A22007-11-22
WO2012018603A12012-02-09
WO2007133912A22007-11-22
WO2000022002A12000-04-20
WO2000071590A12000-11-30
WO2003051988A22003-06-26
WO2012018603A12012-02-09
WO2000009603A12000-02-24
WO2001046107A12001-06-28
Foreign References:
US20110172338A12011-07-14
US20150125334A12015-05-07
CN103709737A2014-04-09
CN105711104A2016-06-29
US7569273B22009-08-04
US20030081599A12003-05-01
EP1059342A12000-12-13
EP0712882A11996-05-22
EP0752432A21997-01-08
EP0086397A21983-08-24
US6025307A2000-02-15
US6103843A2000-08-15
US6126849A2000-10-03
US5229480A1993-07-20
US5763552A1998-06-09
US5688884A1997-11-18
US5700859A1997-12-23
US5895799A1999-04-20
EP1097948B12011-06-29
EP1148072A22001-10-24
US4349650A1982-09-14
US4120608A1978-10-17
Other References:
B. WENDEL ET AL.: "Additive Processing of Polymers", MACROMOL. MATTER. ENG., vol. 293, 2008, pages 799 - 809
J. SCHEIRS: "Modern Fluoropolymers", 1997, WILEY
ASTM D1646 - 07, 2012
Attorney, Agent or Firm:
GEISE, C. Michael et al. (3M Center, Office of Intellectual Property CounselPost Office Box 3342, Saint Paul Minnesota, 55133-3427, US)
Download PDF:
Claims:
CLAIMS.

I . Method of producing a ftuorapolymer article comprising subjecting a composition to additive proeessjpg la an additive processing d vice containing at least ons energy source, whe^in.tfifc com osition corn rfees fliiaropolyraeF partic es and .at binder material capable of

exposed to: the energy sou ce of the additi e processing device and .the method comprises subjecting a part of ihe composition to exposure of the energy source to form a layer and wherein the Ouoropojyiner is a fiuor¾elast0!«er.

2. The method of claim 1 e ein the eort'vposiifcm further comprises one or more curing agents for curing the fl mroelastomer, and the met od urther comprises subjecting the fluoroeiasiomer to curing,

3 The method f claim I further comprising removin the binder material,

4, i e method of claim ί wherein

from tetraflisoroethene an one or mere comonomers selected from hexai¾oroprope«es virsylidene tliiOride: and one or moi* pe viorinaled alpha olefin ethers corresponding w the formula

wherein n represents 1 or 0 id W represents a linear or branched,,cyciie. or aeyelic perfluorinated aikyl residue optionally betpg.;int¾rmpted once or f»ore: than once by an oxygen atom andW preferably having less than i 2 carbon atoms, more preferably having up to 7 carbon atoms,

,1, The- method of efaim 1 wherein the fluor^elastpmer has a

.(TK).Qfiess.than,2:5°C.

6. ite method of claim i wherein the binder '.materia! is polymers-able, and binds iltioropolymer particles b polyhref zirig upon exposure to the energy source.

7, The method of claim 1 wherein the binder materia! is pofymerizable a-ttd binds fluoropolvmer particles by polymerizing upon exposure to the - energy source comprises and comprises poiv!serizable unsaturated: bonds.

.8* The metho of elairn. 1 where the- binder materia i is gelymenzabie, and; binds fiiioiiopoiymer partieies. by polymerizing; pon exposure to the energy source and wiierei the composition is a dispersion of the fluoroeiastonier in a fluid phase.

9·,· The fti thod; Of claim 1 he e the binder material is pol w lzah! , and binds fTuoropoly er particles b polymerizing ypOn eXposure to the energ source and wherein the composition is a dispersion of the fl:uoroeiasti?mer in a fluid fjhase and wherein the polymerizabie hinder comprises polyraerixable groups selected, from actyiate and methscry late; groups.

10; The method of claim ! wherein the bind er materia!: i efv riz blej and hinds

fluofQp Iynjer particles b polymerizing upon exposure to the energy source arid wherein the composit ion is a dispersion of ihe flimfbetasio er in a fluid phase and wherein the poiyrnerizabie b der comprises pblymerizabie groups selected from silane groups.

1 ] . The method of Giaii.ii 1 wherein th binder material is rxrlynierizabie, and binds iliioropolymer partieies by.-$Qjyraertzifl¾ .¾|&n:.'exposui: to.ihe- ener y source and wherein the composition Is an extrnda le composi tion.

12. The method of claim 1 wherein the binder material is polymerkable, and binds fltsOropoiymer particles y polymerizing upon exposure to the energy source and wherein th composition is an extrudfibte composition and wherein the poiymerizahie. binder comprises poiymerizabie .grou s selected fr m: aerylate and methacrylate .groups.

13, The: method of ciahn I comprising the steps;

( i) providing the composition containin he Buoropolyiner partieies and the binder material and optionally other ingredients and wherein the binder material is poiymerizaMe, and bind iluoropoiymer particles . by p lymerizing upon exposure to the energ source;

(it) causing the binder material to polymerize and to bind fluoropoiymer particles By either fa): directing energy from the energy source of the dd itive niahufaetunng: device to a selected location of the 3D pri able eOmposition nd causing the binder material to polymerize and to bind: fluoropoiymer particles in the selected location; or ( by. direciirig a selected location of the TD printable, composition to the energ source n*! causing the binder: material to po!ymeriae and to bind fluoropoSymer particles, o a combination of (a) and (b ;

(Hi) directing either (c) the energy source away from the 3D printable composition of (d) direeting the 30 printable .composition away from the energy source or both, to avoid the binder materia I polymerizing in t e non-selected locations. r a eomtomati-On of (e) and (d):

iv) repeatin ; steps (li) and (in), and if necessary also ste (i), to form- multiple layers aftd create: an rticle.

14, The method of claim 1 wherein the binder materia! melts or I iquefies upon exposure io the energ source and binds the fS u !^poty e partie les. ί 5, The method of claim I where i - the- binder .'material melts or liquefies upon exposure to the energy source and binds the fl orepoiymer particles and ooffiprs es organic partieles selected

polyethylene glycols■ melting between 40*C and 180°G and polymerized or eross*i'inked aer iates, medtacrylates anil combinations thereof.

16. The method of claim 1 wherein the binder materia! melts or liquefies upon exposure to the energy source and binds the fluoropoiymer particles and comprises -organic particles selected

%0

polyethylene glycols melting bet een -'40¾ and \ SI)CC anel polymerized or cross~lini:ed aerylates, methacry!ates and combinations thereof and wherein, the composition is a solid composition of particles.

17. The inethod of claim J wherein the binder materia! melts or liquefies: upon exposure to the- energy source and binds the fluoropoiymer particles and wherein the composition has been extruded into a filament

18. The method of clai 1 wherein the binder material melts or liquefies upon exposure to the energy source and binds the fluoropoiymer particles and wherein the composition has been extruded: irito a filament; and wherein in the energ source comprises a heated extrusion nozzle, through which the corriposition is extruded.

19. The method of claim ί comprising the steps:

providing tire composition containing the fluoropoiymer particles and the: binder materia and optionally other ingredients and wherein the binder material melts or liquefies upon exposure to the energy source and binds the fiu-oropoiysner particles;

(ii } causing the binde material to melt or liquefy and to bind fl noropoi ffier particles by either (a): directing energy from the energy source of the additive

mantt&cturirtg evice to a se lected location of the 3D priritaofe composition and causing ."the Mnder materia! o melt or liquefy and to bf ni iluorepolymer particles1 in the selected location; or (b): directing a selected location of the 3D printable composition to the energy source and causing the binder material to melt or iiqtsefy and to hind Hueropolyrrser particles, or a eoirtbination of (a) arid (b);:

(lii) directing either (c)'th'e energy 'sem ee awa from the 3 printable oorsposiiiorr or (d) directing the 3D printable cotiiposit ion away from the energy scarce or both:, to avoid the binder material to me!t o liquefy a d to bind fiuoropo!y er particles in the non-selected locations, or a ednibination of e aiid (d);

•(iv) repeating steps (ii) and (sii), and if necessary also step (i), to form rntdtipie layers a create an article.

20. A composition for producing; ah article b additive processing in atra ditsve processing device, said composition comprising ifluoropoiymer particles, optionally one or more filler, and binder material capable of bmding the ffuoropoSyrner particles upon exposure, of the binder material to energy front an energy : source of the: additive processing device; wherein the iiioropoiymer is a fltioroelasiorfter.

2Ί-. The composition of clainv St) wherei the I uoroelastomer. comprises repeating units derived from tetrafluDroethene: and one or more cotnonoffiers selected fr m hex fiyoroproperse,, vinyHdene finoride and: ne or more: perflHorhsated alpha olefin alters corresponding t the forrfuiia

wherein n represents i or 0 and 0 represents a line r or branched, cyclic or acyclic perfluorinated a Iky! residue optionally being iiiterrnpted once or nft ir .iba.rt .oinee¾$' aft; oxygen -atoni and i* preferably having less than lg carbon atoms,, more: preferably having up to 7 carbon atoms,

22. The composition of claim 20 wherein the flnoroelastornei" has a glass transi tion temperature o f less than 25°C-

23. The composition of claim 20 wherein the fluoropoJymer particles have an average particle size fDjo of from 50 to 500 nm.

2-1. The composition of claim: 20 further comprising one or more curing agent: for curing the |Ί uoroelastomer.

25. The composition of c aim 20 being a dispersion of fluoropoiymer particles in a, licptid phase and wherein the binder material is pedymerizabte: and comprises poiyrneroabift groups selected fr t aeryiaie: and methacrytat ¾iOups,

26. The composition of ciaiifi 20 Wherein the composition is m extnsda Se com osition

27. The composition of claim 20 wherein the binder material ree!ts or liquefies «ροη exp su e to the energy source and . comprises organic particles selected from wax, sugars, dextrin s, and thermop astio ol ers melting etween 40¾ and ! SO 'SC,

2:8, The composition of claim 20 wherein the binder materia! m lts or liquefies upon exposure to the energy source; find comprises organic particles selected from wax, sugars, dextrms, and thermoplastic polymers melting betwee 0PC and I SO °G, polyethylene glycols melting between 40°C and 1 §iPC . and polymerized or cross-linked aery laies, met aorylates and. combinations thereof and wherein the; composition is a solid composition of particles:.

2¾>. The c mpo ition of cl im 2 wherein: the binder material me ts or li^uefe upon exposwe to the energy s u ce and comprises organie pariieies .selected fro : wax, snga .

■dextrms, and thermoplastic polymers meltin between 40°C and 180 ° and wherein the composition is a solid composition.

30. Λ co osition comprising: a 3D-prinied: flyorQetagomef ,

3 '],, The composition of claim 30 being obtainable by he method, of clam). 1 ,

32 An article comprising a 3D-printed fiuoroeii^ioi r,. the article being selected from friction bearings, piston bearings gaskets, shafrse lSi t'iRg ls seals, washer seals, 0-rings, valv seatSj connectors: and lids.:.

Description:
AI>l>mVE PROCESSING OF FLiJOROELAMMERS

Field

The resent disclosure relates to additive processing of ITuoroelastomers, to fluoroeiastomer articles obtained by additi e pioeessing. and to flooroelastoBler compositions useful for additive processing.

Backgrosiat!

Fluompoiyrners ape widely used as raw n½t -&!$ for their chew seal inertness, in particalar for ' articles: reqoiritig tow friction, properties arid /or inertness to elwm real reactivity, heat, or both,

Fiuqropoiymsrs are typically classified into thermoplastics, non-melt proeessable fluoropolymers and eiastotners fsonietin es also referred to as fluoronihbets),

F|«orotfeet¾oplasties can be roce sed by co vention l me.it shapirrg raetliods, such as rnieetioit moiding and extrusion, Fluomthen¾oplastieS : typ!«aliy are ^^i mers.-0f^t^fiu0ro^>fteri$frFE) ith one or mo other perfluorihaied, partiall " flttarj hated or non-fliiorinated comonomers. Copolymers o TFE and perf!aormaied alky! r al y! ethers are known in the art as PBA's {perfliiorinated alkoxy polymers). Copolymers of TFE and liexafiuoropropyiene (flFPJ wh or withoiit other periyorinated comonomers are known in the art as FEP's {fhiorinaied ethylene propylene). Copolymers of TFE, HFP and vinylideneflacM'ide .(VDF) are know¾ in the art as TMV. Other types of nielt-processabie

©orop0 ym¾s are based ;m ' vinylideneflaoride omo- e GOp0lyi¾ers, known in ti¾e art as FVDF.

Copolymers of TFE and ethylene, are known as; ETFE.

Non-melt proeessable fiuoropo!ymers include homopdymers of TFE or copolymers of TFE with other copolymeriiable perfluoriftated mortomers, wherein the atnountof eomonomerS: is limited to less than 1 %wt Such TFE homo-arid copolymers are referred t i the art as P FFL PTFE has soeb a high: melt visco ity that it cannot be processed by eonventionaFmelt processing techniques suc as extrusion, injection. molding or blow molding. Instead PTFE articles typically are prod need by paste extrusion, or by sfeteris ; to produce blocks or billets which are then shaped into articles. Fo e anipi-e . : by -§l«v¾g, . tjg^Rig, machining |i..e< < subsiraetke methods where material is removed to shape : articles).

Hu^roelastorners, typically are copoiymers of TFE and at least one other fluorinated comonomer, typieaily an alpha-olefiB and have a glass transition tem ature beiow 25°€< ost eo mon!y used comonomers inclade fiFP and, VDF or perOuorinated alkyf viityl ethers (PAVB's), Fluoroe!astomers are curable into a th ees! imensional network to produce tuhbet-fike materials (also called ftso rubbers). Fhioroeiasferner articles are typically shaped b die cutting or injection moldi g,

In WO2007 l 339l2 A2, : ari additive manufacturing process for Special thermoplastic

fTuoropolymers (PVDF and . PCTF) are described but ej aniples are not provided, in CNF037Q 737 A. and C 10571 1 104 A methods for 3l> printing are described where the use of PTFE is mentioned. The materials are processed by irradiating a polymer powder with infrared or lasers and melting the, powder in selected areas exposed to trie IR,-- or laser trradiisi!dn, These methods are Mnown in the art of 3D-prmtiof as laser melting or lasersintering, in US 7^56 ,273 82 a different method is described that h reported to be suitable tor PV ' F * Emn ies ar also sot provided. TTie method described irr ' lJS- 7,3-6¾2¾ B2 involves adding a luid through nozzle to a solid eornposition comprising the polymer and an adhesive paritco!aie: material The ; articulate -material tjeeomes adhesive upon co tact with t e fluid and thus is reported to create an article by distributing the fluid on selected areas.

There is,a need to provide lluoroelastomer articles hy additive manufacturing, in particular for c! irabic or cured fiuorcpolyniers.

Summary

In one aspect there is provided a ethd of -producing a OuGrop ymet article comprising

energy source, wherein the -composition comprises: lluoropo!ymer particles and a binder material capable of binding the ftuompo!yroer particles to fmm a layer in a part of the composition that has been exposed to the energy source of the additive processritg device and the method comprises ' -subjecting a part of the composition to exposure of the energy source t f rm a layer and wherein the-fiuoropolymer is a iliioroefastomer.

In another aspect there is provided a composition for producing an ariicie; by additive processing in an additive processing device, said composition comprising fiuoropoiymer particles, optionally one or more filler, and a binder material eapab!e f binding the fiuoropoiymer particles upon exposure of the binder material to energy from an energy source of the additiv processing device; wherein the fSijOropolymer & a fiuoroe!astonrer.

In further aspect there is provided a composition comprising a 3D-printe fluoroelastomer.

In yet another aspect there is provided an article compri iBg a ,315-prinie -fitSoroeiasto er, the article being selected- from friction bearings, piston bearings, gaskets, shaft seals, ring Hp seals, washer sea Is, 0-ringS; val e seats, con nectors : a sid lids .

Detailed Description

t e present Applicants have observed that it is difficult to create ftuaropoiym r articles, in articular fSuoroeSastomers,. having:;a. cornplex de$¾n ' wsiW tfi^ ' ^dfti^ateethoi lSi.^ iiJ -¾£ ic!e : § by removing excess - ' fiuoropoiymer (for example through skiving or die cutting) asies expensiye fiuoropoiymer material,; Articles rod ced by injection moldifsg are less wasteful, however the construction of molds can be expensive and time-consuming. Rapid prototyping to identify optimize article designs by traditional methods, therefore, can fee economically impractical.

There fore, there is. a need to provide alternative, production methods for producing -fiuoropoiymer articles.

Before any embodiments of this disclosure are explained in detail, ft ¾ to be understood that the disclosure is not lim ited in its application to the details of construction and the arrangement of components set forth in the following description. Also, it is to be understood that the phraseology an terniihoSpgy used herein is. for the- purpose f description. Contrary ¾ ^

'including," "containing " , "comprising," Or "having" and variations thereof is: meant t encompass the items, listed thereafter and equi alents thereof as well as additional iiesiis. The use of ' * a '? or "an" is meant is intended to he an abbreviation and to- expressly disclose th vaiues hetween the ϊ% and such aa ; for example, 2¾ , 40% r !0%, 30% : f.5 %, 3.9 % and so forth.

All references cited herein are incor orate by reference unless stated otherwise.

January 1 , :2016, its case a norm had expired before !anuary 1 , 2056 the most recent active version is meant,

The present Applicants ha e.found »f-¾os¾> ' eja¾dme^artictei. can be prepared by additive processing. The fSuOfoelastoiri-efs are provided as a composition thai Is suitable for additive prt essiisg and can then be processed into a three dimensional article by ad iiive proeessii g, t ically, in an additive processing device. Various known additive processing techniques may be used and also various known additive prQCessiog dSvices or: 30 printers may be tssed. :$uck. . 3D priutabie composiiiofis conlaift the fluoroeiastomer and -additional materia] that is capable of bmdirig tliioroe!astoroer particles into a volume element or a layer either by -.ft) melting, or liquefying r («:} by polymerizing, or solidifying upon die material being exposed to an energy source, typically the energy sout-ce,of the additive processing device. Fiyoroe!astoiner containing layers may be: created successi vely io f rm a. three-dimensional -object After the creation of the article in the additive : processing de iceithe. additional material may be removed, typically by heat treatment which may include degradation or combustion. This step may be followed by

An advantag . of the methods provided herein is that not only prototypes of fluoroeiastomer

be created that may not be available through conventional flsoropolymer processing or only at higher costs.

The methods provided herein are also less wasteful ^c us^::« ' nr^cted ' 3 : fintitbte:-^m ^$¾ton^ may be reused hva next 3D print run,

Addit i ve processing

Additive processing, also known as "3D printing", ''additive manufacturing (AM)", refers to a proces to creat a three-dimimsionai object b sequent deposition of materials , in defin d areas, typically by generating successive layers of material, The object Is typically produced under computer control- from a 3D model or oiher electronic data source by an additive printing device typically referred to as a 3D printer, Die term *'3D printer" and ^additive processing .device" are nsed herein

interchangeably and generaliy-refer te a device by which additive processin can be carried out. The terma "3D-prihlmg" and. ''S -printahle" are-, used likewise and mean additive processing and suitable for additive processing.

Additive: processing devices are devices by which seq ential deposition of material in defined areas can be achieved, typically b depOsitiorj of volume v nts, such .ss- layers.. Successive layers . are 5 built u ,

Typically an additive processing device is eomptrter-eoMroiied and creates the desired object based on an electronic iinage of Che obj ect to be crea ed. The 3 D printer contains an energy sot! ree that applies energ y to a iDea!ised area in a 3 »prihtabie composition, T!ie : energy applied rnay hfe for ' exam le* heat or irradiation or both. The energy source ma include a light source, a laser, e-beam generators, 10 generators and other sonrcing capable of focussi ng energy to: defi d areas of the jD-prfntable

composition. The energy source may e moved t defined areas: over the : siirfeee ©f the 3D printable cotnposition, typieail under computer central.

The additive printing device typically also contains a platform that can be moved into the 3D-

! 5 Typically this is also done under eompiiter control. The device ma farther contain: a device such as:a wiper blade or an injection ozzle by w ich new printable material can be applied over the layer formed for successive iayer~on-layer building, Support structures: rn ay be used and later removed In case : t¾e object to : be created is complex requires stmeiyrai support during its creation.

Additive proeessirsg techniques are known. Objects can be created from liquid 3D printable0 compositions or solid 3D~pr|ntable compositions depending on the additive processmg method and

device used.

The 3D pri.n table compositions provided herein: contain fluoropo!ymers and one or more additional materials. Depending on the additive processing technique, upon exposure to the energy source of the additive processing device * the additional material eithe {i):me!ts or Ι¾¾«©ί¾ . δΐ-, -or. ' {ϊΐ -Siilidifites. jt?r 5 polymerizes: and binds fiuoropoiyffier particles into a volume .eleme t or a layer. Such one or more

additional materials are therefore also referred herein as "binder mater ",

In one embodiment of the present disclosure the layers are. created from a solid ex o ition; The 3D printable composition is typieaily provided in the form of particles, for example in the form of a powder, or in case of the tl lament deposition process, in the form of extruded filaments, The

Q fluorapolymer and: the binder materia! ma be present as particles or the ft tioropoiymer particles: ma be coated with. he binder material. The fluo.r¾polyiPer particles a¾ : fu : sed : .seieetively hy bringing the: hinde material to tie- elt ' (or liquefying it) using an energy Source, typically, a Neat source. .Depending Oft the low: Heat source may be . used. A laser may be ased in eas of selective layer sintering (SIS) or selective layer mel ting (-5 IM , or an electron; beam In case of 5 electron heani melting (BB . If lower temperatures are; sufficient tor the formation of volume elements through melting or liquefying, heated wires and thermal print heads may be used (also referred to as "thermal printing-'),, Processes may include one or more theratal sources for inducing fusion between powder particles, : a .method .for control ling powder fasion to a prescribed region of each layer, a«d a mechanisms i¾r addin and siroaothing powder layers,. Fusioa iwechaftisms can be based on solid ^ sfate sintering, chemkaily iiidueed binding, liquid-phase sintering abd full melting or combination thereof.

These methods use arc energy .source to fuse particles into a mass that has a desired three- dimension ' s! shape. The focused energy sourer selectively fuses: owdered material by scanning cross- sections generated from a -D digital description of the part (for example from a CAD file or scan data} on the surfaee of & powder raised depending on the design of the 3D printer) fay one layer thickness, a new layer: of material is applied o top, nd the process is repeated until the part is complete, in selective laser sintering. (S-LS) or niching (SLM), typically a pulsed laser is used and in EBM an electron beam i used, in 3D thermal printing a heated; wire or a thermal print head or other heat sources may be used, The heat roay be generated for example, by electricity or irradiation or other appropriate means of generating increased temperatures. In the process of the present disclosure the binder material nielts or IrqtfefieS- or Othfervvisfe -si rtifican iy reduces: its viscosity upon exposure to the energy source thus binding; the tluoropolymer particles into a volume element,;

The■ .processing device, may preheat the bulk powder Material in the powder feed Somewhat below its melting point, to make it easier for the energy so«rfcC to raise the temperature of the seieoted regions the rest of the way to t e melting point,

Directed energy deposition (DED) processes deposit a material (usuall a powder) and provide energy to process thai material through a single deposition deyice, DED processes ena ie the creation of parts b melting material as it is being deposited, not b melting material that is pre-laid in a powder bed. As a focused heat source* a laser or electron beam may be used, if less energ is required to melt the material also another heat source, for example one or more thermal print heads may be used, in eXtrysioh-!ayeFct deposition s stems ¾e. t fuse filament fabrication systems and other ielt-exirusipn additive manufacturing processes) articles are produced layer-hy-layer by extruding the 3D-prmtabie composition through an extrusion head. Movement of the extension head with respect to the substrate onto which the substrate is extruded is performed under computer control, i accordance with; the build data that represents the article, ..for example a CAD file. The composition can he . extruded through nozzle carried; by an exte ion head and deposited as a sequence of roads on a substrate in an x-y plane. The roads can be in the orm of continuou s beads or iti the form of a series of droplets (e.g. as described, f r example: in US Patent Application 201 ¾8 !S99). The extruded, composition fuses t previousl deposited composition as it solidities upon a drop in temperature. This can provide at least a portion of the first: layer of ie three-dimensional, article. By ehangingthe position of the: extrusion head relative io the first layer additional rows can be repeatedly build. This D-priming method is also known under the ■term "fused deposition modelling or "FS ": The compositions provided herein may als be used In FDM, in whieh case they am formulated such that they can be extruded, for example as extrudable solid compositions or as extrudable: pastes. The. binder material typieaily melts during the extrusion proces abd the composition is deposited on selected locations where the molten binder material may solidify and thus binds the fTuoreieastomer particles. in another embodiment of the present disclosure the layers are formed by solidifying or polymerizing a hinder material, t p call from a liqi eonipos^ioh or an extrudabie: paste i controlled reas, for example through polymerisation initiated by appropriate irrkliatiom

This: type of additi e man ufafituring technique is generally referred t as stereo! ithography (St) or vat polymerization (VP , Stereo! ithography is an additive man u&ct tiring process that works b iocwsing electromagnetic irradiation (including;, for example, irradiation with ultraviolet light (ϋ¥£) on to

or com uter aided design software (CAM/CAD), the irradiation is used to draw pre-programmed design or shape on to th¾ surface : of the JD-prin able composition. Because the 3 »priniabie composition is reactive to the irradiation, the compositio te solidified or gels and forms a single layer of the desired 3D object on t he areas exposed to the irradiation. This process is repeated for each, layer o tire design under ti¾:3D object; is complete. Typically, the 3D printer used for stere lithogfa hy eontains an elevator platform that descends a distance equal to the thickness of a single layer of the design (typically 0.05 mm ½ 0.15 trim); into the photopoiyroer vat Then,. resin-filled blade may sweep across a cross section of the: layer, re-eo ng it with fresh material. The subsequent layer is traced, jointftg-tbe previous layer...A. complete 3 D objec t can be formed: using this process,

Dependirig on the design of the additive processin ^

lowers the -build platform further than one layer or volume efemefit so that the material is able to easily flow over the pr ious la er olume, element. Upon ireturniag tO ih©½sired step height, the previous layer is uniformly covered, The subsequent layer is traced joining, the previous layer. A complete 3D object can be: formed using this process.

nstea f irradiation with UV, irradiation with other wavelengths may be used,. or example from the visible or invisible, light (e g. IR) and including X-rays and s-beams if a polymefizabie material is chosen that is reaaive ^

irradiation. Conditions for effective irradiation may vary il the type of irradiation and the type of poSymerizabie maierials cbosen, Polymertza e materials and polymerizatii¾ri : initiators may be selected that are responsive to : various types of irradiation for example to irradiation with visib¼:<>r. invisible lights. For example irradiation with light of wave lengths from i f) to 1,000 nm may be used. The irradiation may be monochromatic or polychromatic depending on the reactivity of the poiyfiieriiia&le system chosen.

UV irradiation,^ between 1 and 10 nm, UV irradiation may be generated front a U V source, like a laser, a mercury lamp o tJV LEDs, UV USDs (light emitting diodes, LED) are commercially available that produce monochromatic irradiation at wave length .of 365 nm, 385 nm and 405 nm within:: an errormargin of It) nm. Isfrarsd irradiation typically includes irradiation with electromagnetic waves of a wave length from 1 ram to 750 nm. Irradiation with between 4 ] 0 nd 7<S0 nfri.

The print bie composition comprises a .binder material that is reactive to such IrT diailon with electromagnetic waves by polymerization (or reactive to polymerization initiators that are reactive to such mediation}.. The pfici able eomposirioiis may thus cont-tia one or more polymerizable binder materia! and, o onally,. owe or more pol mentation in itiators. The polyme ization m itiators used are act ivated by exposure i the irradiation from the energy source of the printing device . and initiate polymerization of the bi nde material which hen increases its viscosity, gels or sotidife.

in a variant of this method the 3 ' D-priritable composition: .eohtaimftg ' a polymer izable binder is applied as extrudahie composition, ' typically a paste, th ough a nozateai m m m head to a selected location. Polymerization is carried out as described above tor the stereoiitbography process at the selected location but ma already initiated or completed during t he eximsio onto, the: selected location. This method is referred to as "paste extrusion". The container containing the 3D printable composition m y be heated to improve the . surface quality of the extruded materi aS .

Depending on the complexity of the article design supporting structures ma be attached to the elevator platform to re vent, deflection or dela atiors: due to; gravity and : to hold cross : sections in pi aee in order to resist lateral pressure from th resifi-fiiled blade.

The methods provided herein cart be carried out in known and: eommere sall ay ai (able additive printing devices. Typical known methods and their 3D printer have heenidescrihed, for example, in "Additive Processing of Pol me ^ by B. Wendel etal ,i« M rmml . Mutter. .E g. 2θί¾ ^ - . Examples of commercially available 3D printers include, but are not limited io 3D primers from A $16 ' A * Annaheim, California, USA or vat polymerization printing,and : ftom BLXiEP IKrBR, Copenhagen, Denmark for powdered bed priming with thermal, heads. Printers for paste e trasiotis are commercially available from Hyrei 3D, ¾*orcro¾ 6A 30071, . for example, model Hyret System 30M printer with a ¥©t«25 extruder head. Printers for filament extrusion (F M) are available from Stratasys Direct inc., Valencia,€ A 91355, for example model Maksrbot Replicator -

Fluoropoiymers

The f!uoroppiy«iers for use in the present disclosure contain repeating ' .units d i ved from attenu ted or perfiuorinated monomers,. Suitable .fluarop iyiners for use: in the additive processing methods provided herein include curable fluoropalymers, i.e. fludroeiastoracrs.,FSnoroelastomers . are: conveniently prepared by aqueous eniulsion polymerization as known i the art. Alternatively, ilyoroeiastomers: may be prepared by solvent polymerization including organ ic.solvents and inorganic solvent like liquid C b or by suspension polymerization. Suspension polymerizatio may be carried out in aqueous m edi a without using em uisifiers. These methods : are also known in the art of making

;f1tK>iOpoiyTOers.

The fluofdelasfomers are typically prepared by aqueous emulsion polymerization and: are obtained as aqueous dispersions although methods have ..been described where the elastomers can be prepared: withOtit tluorii ated emulsif!ers. Typical emu tsjfiers include those that correspond to the forinuia

Q- T .R wherein Q re resent hydrogen, CI or F, whereby Q ma be present hi a terminal position or not, Rf i'epreaeiits a linear or cyclic or branched perfluerinaied or partially tluorifiated a!kyltoe havihg 4 to 15 carbori atoms, 2 presents an acid aBio.n, such as COO " pr SOy and r i-esetits a ca ion including an alkali metal anion or an amntoojuro ion. Examples fliiorinated euadslfiers include those described in BP 1 5 059 42, E 712882, EP 752 32, EP U 397, US 625,107. US 6,1 : 0¾843, US ' 6,I 26,S49, US

5,229,480,. US 5.763,5 2; US 5,68:8, US 5,700,859, US 5,895, m OO0/22QO2 and WOW ? i 590.. The fluorirsated eroulsiiiers may be removed, i the work up procedure, lor example, as described in oo3 05J Sa.

Eiuoweiastomers are curable nuoropolymers. They cat? be cured (cross-linked) into a ffiree-

10 dimensional network by reaction with curing: agents, They typically ee-niam at least 30% by weight of flLiorine v more prsfembly atleast 50% by weight of fluorine, ffiosi: preferably at least 60%^ b weight of fluorine, and typically between 38 and 75% by weight of fluorine (based on the tmi weight of the polymer);, T& fluorine content may be achieved by selecting: the co-monomer and their amounts accordingly. Typically, the e«f able: fitioropo!ymsrs are amorphous. enerally, they have a glass: transition i 5 temperature (Tg) of less than 2 ' 5*C, preferably less than -105°C and more prefera l less than -20° and most preferably less than -35 a C The curable fluoropolymers described herein ma typically Mve a Mooney viscosity pi, i+10 at 12 i*C) of from about 2 to about ISO, preferably about 10 i to about 100, more preferably from about 20: to about 70.

The fluoroelastomers may contain ewe sites derived from cure site, monomers. Typical cure: site i monomers include copolym rizabie, preferably perfluori ated, co-monomers containing one or more iodine r bromine groups. Other cure sites include iodine or bromine end groups in terminal polymer

cure upon reaction with a peroxide core system. Examples, of suefe ffuoroeiastomers are described, for example, in WO2 i2/0! 8603 Al or EP 1 097 948 81 , The Jvwroeiasiomei-s may contain cure sites 5. sn sccpt ibie io bisphenol earing, r cure a¾e: groups susceptible to : ammonium generating; eompotmds, for example by formation of riaxmes. Such cure-sites typically include nitrite (*C ) groups. Examples of such curing agents and susceptible elastomers are described, for example, in WO 00/09603 Αί . Examples of snita ie fluoroelastomers include those described, : for example, in W0 ii 12/01: S¾03 Al of EP 1 097 94 S B E

; In one embodiment tbe : fluoroeiastoroers are perff ueroeSastomers,: such as polymers f TFE and perHuorovinySethers that may contain: optional oxygen atoms in the perfluoroalkyl chain (PAVE) and polymers of TFE, HFP and one or more PA ' fE. Typical examples of PAYEs include but are not limited to perfluoromethyi. vfnyi ether (P¾ ¥E), erfluoroprOpyl vinyl ethers (PPVEs) and aikox vinyl ethers including those of the general form u la: 5 CF; :; EO (R R D) S! (R¾0) ; n :f where J½ Mid R are different linear or branched perfiaoroalkylens groups 1 of 2-6 carbon ■■ atoms* in and n are independently 0- 1 Q, an M i$ a f>erfl«5roa3kyi. group of ί -6 esrrhen atoms. Another class of

where % is F or CF n is and. Rf is a perfiisoroalky ! group of Ufs carbon atoms. A other class of perfluoro (alkyl vinyl) ethers includes: those ethers wherein « s & or ί and Rf contains 1 -S eartjop aioms, Addifiortal perfluoro (afkyi yirry!j ether monomers ioelude. compounds of the lorauda

where m au:d n indepen eniSy are MO, p represe&Is .9-3, and ,x represents: 1-5, Other exa ipfes: include those of the formula CFj-CFOGFaORi wherem R is C2~€<, JijK&r

groups that ' may optionally contain one or more ea¾:rsary xygen atoms as described, for example, in FP 1 148072. Also the ally ! analogues may be used* he. polymers with CFa-GFCF^-O- unit instead of me vinyl unit CFi « FO^. Parti etitar xam es: of perfhioro iriy S ethers inci ud¾:

F2C-C -O-(CF 3 ) '. s r0G >,

F : >e-€F-£K€:F 2 ) j-(OG j -F,

F 2 C-C " 0 ' eF (OCF2}3-CF 3 ,

Specific xam ie of s u itafale peril uori nated .ally 1 ether comonomers inclii :

F;5€-CF-C 2:-:0-eFi-© e 2):^ }

PsOC F-CF O-f CP j . 2-OCF3.

F3C-CF-C . ¾-0-fCF 2 :),,-QCF 3 .

F 2 C=CF-C 3-0-C. 2 -(OCFj} 4 -CF; t .

6 F-GF 2 -0-(C:F 2 C>h-OCF3.

.10

Particular examples of erfiitorinaied ajkyi al! l ether PAAE's) Include unsaturated ethers according to the general formu la; . } >•Ci -( -( }R :

IS '

wherein represents a linear or branched, cyclic or acyclic perffuorinated alkyj residue. f may contain up 10 10 carbon atorns, e.g. 1, 2, 3, , 5, 6, 7, 8 S :9 or 10 carbo atoms. Preferably R ! contains up to 8, more preferably up to 6 carbon atoms and most preferabl 3 or 4 carbon atoms. I¾ 5 may be linear, branched and it .may contain or not eohtam a cyclic ami Specific exa ples of R* incfede pej * B«orornethyi 0 (CF^) ; perfiuoroethyj ( >Fs>, p«rfluoropropyi {G^F?) arid perftuorobutyl ¾F > - pf ferably CijFs, C¾F? or <i.

Ferfliiortriated aikyi aJ ly l ethers and alkyl v½y1 ethers as described ove are either commercially available, f¾ ' e^iii >fe : :.fr0m : -Aiiles--Lt4. St, .Feterburg^ Rsssia oreari be prepared aceprdmg to methods described in U.S. Pat. Mo, 4,349,650 (Krespan o international patent application no. WD 01/46107 5 (Worm tit at) or In Modern Fluoropolymers, i. Scheirs, Wiley 1997 and the references citsd therein or by. mDiiificati ns thereof as known to ihe skill d person.

Mixtures of perite vinyl) ethers may also be used, as well as mixtures of the vinyl and ally!, ethers described above.

I one embodiment pe fliioroelastomers . re composed of tetrafi uoroethylsne and at least on 0 peril uoro (alky! vinyl), ether as principal monomer units, in s uch copoly mers, the capo lymeri¾ed

perlHsorinated ether units may constitute from about 15-60 mole percent of total monomer.

In general, the amounts of comofiorfters are selected to give a polymer with Tg of less than 25 9 C, and, preferably a fully amorphous pol rner as is known in the art.

Preferably, the perfluoroeSastoniers contaui CN-cur sites, for example: by CN-group bearing 00- S. monomers (cure site monomers) . In one embodi meat: the perfluoroeias.torBer contains eopolymerjzed units of at least one cute site monomer^, generally in amonnts of from . X -5 mole percen : The range Is preferably between 0.3- 1.5 mole percent. Although more than on¾ type of cure site monomer may be present, most common !y one. cure sfte : monomer is ased and it go ial ns at least ue flltri le su bstitueai

1.0. group. Suitable cure: ite monomers include nitrite-containing ilu finated olefins and nitriie-ebntammg iluorinated vinyl the S Useful nitrite-containing cure site monomers Include those of the formulas shown, below,

n - 2-12, preferably 2*6

CF2-CF-0-[CF 2 -CFG : i -0] 1 rCF 2 -CF(CF i )-CN: where n= 0-4, preferably 0-2;

.FH^OCF^ l -¾,a!¾i « I -4;¾nd.

The 3D-pri«iable coniposftions «say contain curatives, for Curing the i uoroe!aaomer. Suitabl curatives for elastomers with uitrile-eare sites Include, but are hot■ limited to, nitrogen containing substances that decompose to generate ammonia, preferably at high temperatures and as known in the art. S u tabic compounds include hexan ethylene tetmmine, aniidoxraes, am idrazones, . earhoxam ides, phthalantides, amidines and cOrabtftatsons thereibre. Also mm nium salts of organic Ms may be used .

The curatives may be selected for the 3D printing method used. Typically, the articl is created in the 3D printer without activating the curing reaction, i.e. without activating the curative. Curing agents that become reactive: upon thermal treatment -are: suitable for methods usin p iyroef teable Mfiders. that are activated by U V curing.

For 3D printing methods using a binder material that mel s or liquefies curative are used that get acti vated at greater tetpperatores i the temperature applied to toclf o ttqmty fhe binder material, Curin of he article is iypk: ! iy carried, out after the, article has been formed, fo example when-- removing the binder material or dispersing media, like water, in case the ID-printable com ositions, are used as dispersions,

Amount and typeof curatives can be.optimized, dependkg on binder, polymers mi energy source. Amounts of curatives and type of curative will m¾uence-¾e curing speed and properties and can be optimized upon demand.

Commercially available fiuoroelasterner and curing agents may e used.

composition. I ' be compositions are sui¾?ected to additive processing in an additive processing device.

compositions may be ptimized for different types of 3D printers a«d.3D-printing: ' methods,. Additive processin isSi ai o yn^erix bk binder material

in this embodiment the article is formed by using a binder material thai: increases its viscosity upon exposure to the energy source of the additive -processing device. This can be achieved by using a polymeriza ie binder * which , polymerizes upon exposure to the ersergy source. It may either create a solid

Π or it may gel or it simpl increases in :v iseosiiy. The ' W≠st ί$ ' ί τέ^ϋΐ. in -m ff^t & mi Mtt& feiiiii the fiyoropoiymer particles when, polymerized. This keeps t e particles in the selected location to create a volume element.

In one embodiment the tmoropoiyttter is provided in a expositi n eornprisittg one or more binder materials that arc poiynleri zabie. The; composition; ma fu r Sier com prise one or more

polymerization initiator. The polymerization initiator may be activated dy p sure to the energy s ur e and: causes the polymerixable' aterial to polvtiierke, Alternatively (or its: addition), the «i groups : ί the po!ymerizahle binder material may be reactive enough that no oS ne iiati^n initiator other than the ene gy source of the additive processing device is needed to initiate the polymerization. The 3D printable composition may be a .solution bat preferably is a dispersi on containin fluoropo!ymer particles. The particles may be dispersed in ah inert organic medium. Preferably the;f!uoropolymer particles aro dispersed in an aqueous raedih and the 3D printable composition comprises: an aqueou dispersion ' of fiooropolymer particles, The ftuoropolytner content of the compositions is preferably as high as possible; but may be limited by stability of the dispersion (coagulation or precipitation of flaoropoiyniers) or the dispersions may convert inlo pastes. nd polymerization might proceed too slowly to create solidified layers by vat polymerization. Pastes, however, may be preferred in oil ier meth ,: for example m the paste extrusion metiiods, General l ¾ concentrations: of fluoropolymers.ffiay include; bat are not limited to concentrations from -about 20 to 70 %"vvt. based on the total weight of the ; composition, or from 25: to 60%, from about 30 to 50% or frontabout j l to:4S % wt based; on the total weight of the composition.

The poIytoei¾abie hinder material is matched to the energy source or to the polymerization initiator, which is matched to the. energy source of the additive processing: device (3D printer), such that exposure of the 3D printable composition to the energy source allows polymerization to proceed and at appropriate speed hi the part f the composition that has been exposed to the ner y source of the 3D printer.

ie poiymerizabfe binder material ma he dissolved :.or dispersed in the 3T3 printable composition, or it may be a Ikfuid and m boused as dispersing medium for the fluoropoiymer particles: Preferabl the polymerizabte binde material Is dissolved in the 3D~prin½ble. eompositiori. To dissolve r disperse the binder material organic solvents or dispereanis may be used or an: aqueous mediu like water may be used. The organic solvents or dispersarits are preferabl inert. sind do not polymerize or react with the binder o polymerization initiator.

The optimum amount: and type of polymerizable binder materia! may be determined: taking Into account the following: the amouiit of binder material preferably is high-enough such that it allows, to sol ify in the areas where the layers are to be created:, i.e. it. is preferably present n an cHective amount to allow the fbrma ibn of solidified layers of the desired dimensions. Secondly, the amount of polymerized hinder may be ' minimised with respect■ to she fluoropoiymer content io/minimlse or avoid shrinking; of the article durin the working up process.: Also the -formation of voids in the fini hed articles created during the removal of the polymerized hinde material ma be minimised r even avoided. Also the: stability of the fkoropoiyraer dispersion has: t be cous idered: and too.: high amounts of binder material may lead to premature coagulation of tire n:u ropdyraer disp¾S'$ion or&jltrtton. The -binder material is capable to ol me i e to r¾rm a soiid or gel of SwiHeie«i s en ths to retain dimensional stability throughout the creation of the created object However, the polymerized binder ' materia} is not responsible for the dime nsional stabs ity of the finished artfc ' le and can be removed: thermal ly duri n the work . ' up procedure wit hout the articl ^ iKcoming dtmensiofially unstable. The polyaierizable binder material desirably ol merizes fast under the conditions, hi the additive pi-ocessing machine- preferably, the poiyuierisid binder theii lly degrades at temperatures below the decomposition of the elastomer or structurai failure. Preferably, th binder ciiri be combusted at such conditions.

The polymerizatioii should be edntreiled to the areas exposed to the: energy source , of: the 3D pri ter, if necessary and depending on the: energ source used, polymerization inhibitors may be added thai help preventing the poiyme rizat ion from proceeding outside the parts, of the compositions that were exposed to the.eitergy source.

A suitable polymerizabie binder material includes monomers, oligomers or ■■ polymers; with polymerizable groups, preferably end groups. Such .poiymerfzabiie end .■groups ' include groups reactive to electromagnet ie irradiation by. ' poiy-mSriizfction ©rthat'p^Iyinfcr&e .upon ' acti ation .bypo ymeri tfon initiators o r a combination thereof. Suitable polymerization initiators include thosetiiai are activated by electromagnetic irradiation and include rganic or inorganic initiators.

Suitable poSyiiVerizabie binder rnateria!s include compounds with po!ymei¾abIe groups eomprisirt one o more olefvuc unsatuiraiion. ' .Examples include compounds with end or side groups comprising one or snore et ylenic unit,, i.e. a carbon^carbon: unsaiuration (e.g., a carbon-carbon double bond). Examples include end groups comprising .one or more of the roups: selected from vinyl groups

H or Cfij.

Suitable poiymerizable groups include but are not limited to end ' and side groups comprising one or more: units corresponding to the general formula {I)-(IV>:

H 2 C « G{X>-

H 2 C ¾X)-0--

H2C^ ' ( C(~0 or H;C-GX~C0 3 -

H 2 G^G( Oe{Q}- vvherein X represents a hydrogen or methyl group. Examples of polymenza le binder material;; include mono acrylates and mono methaeryiates, i, : e, compound with one; end or sick' group comprising aery ί ate group- or mediaery late group id;g, an

group where X .i§ : I or OH and p^l ^ iafes or poly methyl aery lates, i¾ compounds having more than one end. and/or. side groups comprising an aerylaie or methacryla e group. Examples

5 include:: monomelic, digomeric and polymeric acrylates (i.e. comprising one repeating monomer unit, in case of mono merie compounds:, front more than 1 up IS repeating moii e ic dnfts in ease of Qligomerie compounds and from more than 25 repeating visits ίίϊ ease of polymeric compounds. Furt!mK these compounds comprises at least one aery late end or Side group to quaHfy a.s acry!ates. Examples for

if ) aciy late units a d combinations thereof Acrylates eftmprismg an ¾to ' uii ai¾ri¾f«j!-red ' to alsG,8S

"et oxy!ated acrylates- ' . Specific examples include ethoxylaied or polyeihoxylated -acrylates, for example compounds having one * tvto or three- aefylie end or side. groups. Other exampie&incJude ..aeryiaies having one or more than one aeodate group linked to ad alky ! or alkyJene chain that way be is¾en¾pted oiice or more than once by oxygen atoms, Acrylates include but are not limited to monoaeryiates, diaerylates and

! 5 triacrylates. and combinations thereof " md ud in g their methacryiie equi alents. Spec t fie examples inc! ude bii:t.afe ndt ' i.itnited : fc e i ^iate^

Specific examples include ethoxylate trimeihyiol propane trlacfylaies; (SR I S); polyethylene glycol dimettwcrylate (SR252 , ethoxylated bisphenyl A dmiethaciyia e (SR9036A), eihoxylated bisphenyl A dimethacfy!ate (SR9iB8) ail. commercially available, from Sartorner Americas, Extort, . I>A » USA.

M in one embodiment of the present disclosure the binder materia] comprises a polyethylene glycol di- or triacrylate or a combination of poiyet lyene glycol di- and triacrylaies,

The overalMomposition :of.t e polymerizable material: may be selected so that; the polymerizable material is liquid, or is soluble in a solvent or dis ersing medium used ¾ the 3D-printabSe eempositios,. e.g. water. Further, the overall composition of the polymerizable materia! cats be selected to adjust

25 eompatibiiity wiih the other ingredients of the.3I prmta;bie composition or to adjust he strength, Oexsbility, and uniformity of the polymerized material ' Still further, the overall composition of the polymeri able material can be selected to adjust the burnout characteristics of the polynierized material prior to sintering, Various combinations of binder materials may be possible and are available to the person skilled in the art. Mixtures; of differ nt poiyinerfeabte; binder materials may used. For example W- or poivfunctiona!

39 polymerizable binde materials may be included tfiat generate a cross-linked network. A stiecess ul build typically requires a certain level of green body gel strength as well as shape resolution. A cross I inked approach often fimes: : :allovvs fo grester green body gel strength ta be realised at a lowe energy dose since the polymerization Creates a stronger network; The presence of monomers having plurality of polymerizable groups tends to enhance the strength of the gel composition formed when the printing sol is

35 polymerized ... The amount -of the rnonomer with, a lural ity of the polymerizable 1 gr ups can be used to adjust the flexibility and the strength of the green body, and Indirectly optimize the green body resolution and final article resolution.

1. in the fo!lo ing, exemplary binder mate-rials are ednlerh iated as being: useful as. an alternative to the h>ateriafe described above or in combination with; thet ,

Examples include but are not limited to aei-ylic acid, methacryiie acid beta-carboxj'ethylae;ryla{e,

5 for use as binder or f preparing binder compositions mciade hydfoxyethyi acrylate, hydroxyethyl

methacr late. : yd?oxypropyl aerylate, hydroxyproi^I niethaerylafe, hydroxy! butyl aciylste, and hydroxybutyi methaeryiate, Aery!oxy and metbaeryioxy fiinsliona pol eth lene : oxide, and

pol y propy lene oxide may; aiso be nsed as the : olytTier iiabJe hydrox i-eontai ing moeomers.

An exemplary radicall polymer zabte binder material comprises, ΠΪΟΠΟ- ; . (met acryioxypoly et yleneglycdl:]; suceii ate .

Another exam pie of a radically polymeri¾abk. iji der materia! (aetivitated by a pholoinitiater) is a polymeriza le si!ane. Exemplary: poiynmrizahSe sllanes include :met|¾ctyloxya¾yltriaikoxysija es ; or ac!y iJxyal:kyltri:alkoXysifanes:(e,g., 3- ethacryioxypropyhrim^

S- md 3 ¾ery!oxypropyi)methyMi

iiiercaptoalkyltrialko^dsiianes^e-g., J-mereaptopropyitrisnethoxysiianie);. aryiinaikoxysii:attes,(e>g. 5 styry!eihyitriinethoxysi!ane); vinyisilaties (e.g., vinylmetiw!diacetoxysilajie, vinySdime 4ethoxysilane, vinylmethyldie-^

0 vinyitrn sopropoxy si is , viny tiriniethoxys ilane, an y inyltrisf 2~ methoxy ethoxy)s i lane).

Exemplary monomers with two meihjaeryloyl groups include l ,2-etha«edioJ . diaerylate, 1,3- propaoediot dfaciy late, i ^-nonanediei diaery late, i , 1 ' 2-dodecanedrol. diaerylate, 1 ,4-buia;nedioi diaerylate.. i,6~hexanediol diaorylate, butylene gtyeoi diaerylate, bis lienoi A diaerylaie, dkthylene glycol diaerylate. iriethyiene f lycol diaerylate, tetraethytene giyco:! diaerylate, tripropylene glycol, diaerylate,5 polyethylene glycol diaerylate, polypropylene glycol diaerylate, polyethylene/polypropylene copefiymer diaerylate, peiybuiadiene di(n?eth)acryiafe, pr poxylafed glycerin iri(meth}aerylaie, and neopentylgiy ot hydroxypivalaie diaerylate mo fied caprolactone.

Exemplary mon&raers with three or foiir (meti jaefyldyl grou s include, but are not limited to, trimethyloipropaiie triacry late (e.g., . co mercially available -under the trade designation MPTA- from0 Cytee Industries, inc. (Smyrna, :0.A, USA) and under the trade designation 5K-35 i ( torn Sariomer (Exten, PA, USA)), pentaefytftritol triaeryiate (&g., commercially available under the trad designation M- 44 from : ^artoffier), etlloxyiafed (!) tnmeihylolpropane triaoryiate (e.g., eoaimereia!!y available under the trade designation SR: 5 from Sartomef), ethoxylated (4) pentaerytrs itoj tetraaciylate (e,g.,

commercially available under tie trade designation SR-494 trom Sartomer), tris(2-5 hydrdxyethyl isocyanwate) ir iacryi te (e;.g., con merciaiiy available under the trade designation SR-368 from Sartomer), a mixture of pentaerythritol triaery!ate and peutaerythritoi teiraacryfate (e.g., commef cia tly av a i table, fom. ytee Industries, Inc., under the trade ; destgnailon PE iA an approximately 1 ; i ratio of letraaeryiate to triaeryiate and under the trade designation PE - with an ^proxim tely 1:1 ϊ > of :tetraaery!ate ½: ttiacrylate), peotaerytiiritol tetraacry!ate eoiiwiercialiy tetraacr late (e.g., c mmerckl!y avai! iWe mde the tr de desigiistion: SR-355 fforii Sartomer).

Exemplary monomers with five or: six (meth)acryloyi groups include, but are not limited to, dlpentaenithriiol pentaaerylate {e.g., commerciall available under the trade ^ designation. from Sartomer) and a bexa-fnnetional urethane aery late (e.g., commercial un erthe trade designation CM975 from Sartomer).

Exemplary monomers for use as polymeriitable binders include alkyl {meth)aerylates that have an

include, but are not limited to, methyl (meth)acryiafe s ethyl {roeth)aerylate, s o^

isopropy 1 (mei )acry late, o-biityl {roetlr)aet late, isobutyi (laelh)aer iate, n-penfyl (methjaeryJaie, 2-

ime hiacr latev S-mei&yihesyl (nieth)ac ylate, n-oetyl :(meth)aGiyiate 4 isooetyl (fnet}i)aeryiate. 2<-octyi( et¾ac y!ate. isanonyl {meth)aerylate, isoamyl ( eih)acrylate;.3 ,5- trimemylcyelohexyl { ≤ti¾ cryi ^ n-dee I (inethj ry late, isodecyl Cmeih)acrylato, isobornyi

(meth)acfyiate, 2-propylh tyf (meth)acrylato, isotri eeyi (roeth)aetylate, Ssostearyi {meth)a y!ate, octadecyl ( ethjaerylate, 2 oetyideeyl (met )aer late, cfodeeyl (metS¾acryiate, lawtyi (meth)aciylate, and hepfadecaiiv I (metb)acry !ate.

Optinitjm amounts, of binder material may be adapted to . the specific system used. Generally, suitable amounts of polymerizabfe binder ai-e. from 1 to 50%, or irom,2 to 25%, or from 10 to 20% {weight per cents based on the total .weight of the: compositions). The polymerized binder may have to be removed during the work-up procedure so the biuder material should not be used in a great excess over the tlworopolymer particles as this may cause a structural failure of the article, Optimum ratios of iluordpolymer to pOiyuierizable biiider material depend on the type and nature of the binder materia! but may typically include, but are no limited to, weight ratios of fiu ropolymer to polymerizable ·■ binder material of from 5: 1 to 1:2, preferably from 4; to 1:1.

In some applications, it em be;:advantagepp:.i m i jmiz fie wei ht: ratio of polymerizable binder material ' to fluoropolymer particles in the reaction mixture. This tends to reduce the amount of decomposition roducfe of organic material that needs to be burned out prior to formation of the sintered ariick The amount of bmder may aiso depend on the speed at which the ftueropoiy i er particles sinter, if ¾ sintering proceeds last the combustion gases from the binde material get trapped inside he: article, which can lead to a reduced density and/or to surface defects, hi this case oxitiatios catalysts may be used or the amount binder pay be reduced.

Preferably, the binder material comprises polymerizabJe monomers or oligomers having a molecular weight torn ISO to 5,000 gteole. This may facilitate the formation of a . ' ID-priritabte composition of a favourably low viscosity, one embodiment the polymeriza le binder material is liquid. Other exemplar polymerizab!e binde materials: contemplated herein includ but are not limited to epoxides, and reactive components that ca polymerize to form polyurethanes.

The binde Material is preferably selected such tfeat the resulting: polymer easily degrades, ai the temperatures applied to work tip the article,

Other additives:

Polymer ization Initiators

One or more polymerization initiators that initiate pol merization ' ¾f the ' polyntertzable. hinder material nmy b present in the 3D-printabie eompositk)n> The polymerization initiator gets activated u on exposu e to the en rgy source,: or example, updh exposare ts (JV iirradiation er e-bearti: Irradiation, or h at, initiators: that are activated by trnsduniori : i^ ' V iSi ¼: iSi'- -iinvisifei light are referred to as photomttiaiors. Polymerization initiators may be organic o inorganic. Polymerization Initiators; are known in the art and are eorooiereially available. Preferably, the following classes of photoiitiiiatCir{s) ean be used: a) two- component ' system where a radical is generated through abstraction of a hydrogen atom form a donor com ound; b) one component system where t o radicals are gen rated: by cleavage.:

Examples of phOi.oinitsators according to type : (a) typically contain a moiety seieetedTreut henzophenone, xanthone or quinbne in combinatio with an aliphatic amine.

a moiety selected form benzoin ether, acetophenon, benzoyl oxitne or ;aeyl phosphine.

Exemplary OV initiators include I -hydroxycyei phen l benzophenone (available, for example, wid r the trade designation 'IR A U E: l$$ n from Ciba Specialty Cbem seals Corp., Tarrytewn, Y),:4- - d^yethoxy) ' phenyl-(2*h TO y-2- f»py ketone (available, for example, under the trade

methylpropiophenorie {avaiiahie, for example, under the mde designation 'OARDCUEE Di l i" from Ciba Specialty Chemicals Corp. and b:is(2,4 ^trimethy!benzi>yi)-phehy1posphineoxide (available, for example,: nnder the trade designation "IR AC RE SI*?" fern Ciba Specialty Che icals€orp ).

In one embodiment of the present disclosure -a polymerization initiator used with a

polymerizabie binder -materia! . selected from aerylates. Typically ttves: . polymerization initiator is. a photoinitiator, whieh is activated by irradiation with visible or invisible light,: preferably by UY irradiation. The optimum ameriois of initiator depend on the system used, Typical amounts include but are not limited to amounts of I n> 0.005 or from 0.1 to O.tKlQ l times the weight of the polymerizable bi der used.

The pbotointtiator should be. able to start or initiate the polymerization- ofthe polyroerizable binder material. Typical amounts of photoiniii t ^s) include bnt are not limited to the following -.amounts: Lower amount: at least 0,01 or at least 0, 1 or at feast 0,5 wf,-¾: Opper; amount: at roost .0,5 or at most I S or at most 3 Range-: from 0.01 to .3 or f om 0,5 to 1 ,5 t-%; wt,-% with respect to the weight of the 3D- priniable compositioft. Qther amounts may include,, for example, f m at least 0,00 } ., o at least 0,0] or al least 0,05 wt-%; Upper amount; t most 0.S or at mast 1.5 or at most 3 to 3 or from 9.05 to 1 ,5 wt.-¾ with respect to the weight, of the D^printable composition.

instead of oljTOefixatiqn miiiat rs that are activated b visible or invisible light, like UV irradiation, it is also possible to use initiators that are activated thermally ' or by actinic irradiation. In such case, the energy source of ' the add itive manufacturing device is ap opria ely selected to allow activation of the initiators.

Polymerization inhibitors

' The ' 3D-pnnta le c m ositions may also contain one or more polymerization inhibitors, to help keep.: the polynaerizatiort reaction localized to the areas that have been exposed to the energy source of the ditive : praeessin maeh ne : . Such polymerization inhibitors slow down the polymerization reaction or terminat it. for example by acting as radical seavangers. Inhibitors for ' polymerization with irradiation through light, including UV light are kn wn ih the art as: ''photoinhibitors" and include commerciall available materials such as 2 ; 6^di srt*butyI-4-methyl lTeriol, available from Sigrim-Aldrich, St Louis, M£), USA. Optimum amounts of inhibitors depend on the system of pofymerizable binder materia!, Initiators and efiergy source used. Typical amounts f inhibitors include but are not limited to amounts of from 0.9

Fillers, pigments, U V enhancers and oxidation catalysts

The D-prihtable compositions may further comprise fil lers, pigmentS:or dyes if compatible with the W printer used and the theftnal work -up ' -treatmen Fillers may include butare not limited to silie«n Oarbide,: boron nitridej moiybdenum ^sulfi e slominmn xides, carbon particles, such as graphite o carbon black, carbon fibers, carbon nanotubes. The filler eonteRt ean be optimised to the system used and may typically be between ChO ! to 1.0 % or up to 30 % or even up : to SO % by weight based, on the total weight of the composition depending on the fluorapolymer and binder materials: used. The fillers should be in particulate form and have sufficiently small particle size to allow for a homogeneous dispersion in the 3f printabt composition. To be compatible with the :3p-printable composition the. filler particles adyantage:055sly haye a pattiele size of Sess tl n SOD j«ri, preferably less than up or even less than 5 |t ..

Pigments have to be beat-stable at the temperatures applied in the thermal -work up procedures, i.e. at ieast the melting tem erature', of the non-melt processahle Tiuoropolymer.

ingredients that increase the irradiation, energy from the ener may also be included i the 3© printable composition, For example, by activation through UV · irradiation UV enhancers ("optical brighieners' ' } may be included in the eotogosttidn. These are chemical compounds that absorb light in the ultraviolet and violet region (usually 340-370 mn) of the electromagnetic spectrym, arid re-emit light in: the blue region {typically 420-470 nm b fluorescence A useful optical brightener is Benetex OB-MI . Lakeflfe!d: ct Shwalise, G 30024. lis UV brighieners may l o: help to limit the penetration of the irradiation from the energy sotirce throngh the 3D-prlntable : :eomposition and te control the polymerization to localized areas. Oxidation catalysts may aiso e. included in- the TD^prmtable compositio to accelerate the combustio of binder during the thermal work up procedure, This -may help to create s smoother surface and to avoid the formatio of surface delects and/or inte nal voids. It. is believed thai' feh the combustion of ' he bind r materia! is not completed when the surfac particles fuse during a sintering step trapped eombustlon ses may lead ^for ation 6f raiCRsb«bi>fe¾ ' Or ; -<« icro sr&eks : ' ο«ί the surface and/or interior of the sintered article, The oxidation catalyst may accelerate the combustion -such that the 'combustion gases have evaporated before the ffuoropolymer particles on the surface: fiise. Oxidation catalysts: are described for example in IIS Fat. No. 4, 120,008 an include cerium oxides or other met l oxides. Cerium oxide is: commercially available from Ny col ano T echnoiogies Inc. This also might reduce scattering effects from the UV source.

Optimum amounts of bidder material have to be adapted the specific system nsed. Generally, suitable amounts of poSyme izafele binder are from 1 to 2S¾ f or from i (J to 20% (weight per cents based on the total weight of die compositions),

Qm o more polymerization initiators m y be present in the composiiiori that iuitiate polymerization of the polyme izable binder materia!. The polymerization initiator gets activated: upon exposure to the energy source, for example upon exposure to UV irradiation or e-beam irradiation. Initiators that are activated by irradiation ¾h visible or invisible light are referred to as photoinhiaiors. Polymerization initiators may be organic or inorganic. Polymerization initiators are known in the art and are commerciall available. Typical !y such com pounds include organic and inorganic peroxides, peroxosul&tes and peroxosulfooates. Commercially available photo auiiators: in parti-eular suitable lor use with acrylates include those available under the trade designation fKGA-CW E, i¾r example ¾is-(2,4,6- trimetlrylbenzoyl pheny phosphirie oxide) available as I GACllRH S i from BASF, Charlotte, NC, US A ), i n. one embodiment of the present d isclosure a polymerization initiator is used with a polyraerizabie binder material seleeted from acrylates. Typically the polymerization initiator is as a pbotoimtiator, which is activated by irradiation with visible or invisible light, preferably b UV irradiation^ The optimum amounts of initiator depend on the system sed. Typical amounts include but are not limited to amounts of I to.0.005 times the weight of the poly erixabie binder used.

The compositions m^

to the areas: exposed io th energy Source of the additive processing machine. Such polymerization, inhibitors slow down the polymerization reaction or terminate it, tor example by acting as. radical scavengers; Inhibitors for polymerization with irradiation through light, includin ij " ^ light are known in the art as "photoinhibitors^ and inc!nde coimrierciaily ayailahle materials such as 2,6-di-tert-buty!~4- methylphenoi, available from Sigma-Aldrieh, St -. ' Louis, ΜΌ, USA. Optimum amounts of inhibitors depend on the system of poiymerizable binder material, initiators and energy source used, T ical amounts of inhibitors include but are not limited to- amounfs of from 0.9 to 0.001 times the smoani of po!yniefization initiator (by weight).

Th . ' compositions ma further comprise fillers, pigments or dyes " if compatible with the 3D printer used. Fillers may elude but are not ismited to silicon: carbide, boro nitride, molybdenum sulfide, aluminum exides. and carbon particles such as:graph¾e or carbon black, car o fibers, carbon nanotubesv. The fiUer content can be optimized io the system used arid may typically be between 0.0 ! to 0 ' % or u to 30 % weight based, on the total we ght of the cohipositlon depending OR the fliioro olymsr a¾d binder materials used.

fegredien s th t iacrease : the irradiation energy from the energy may also be included in the 3© printable composition. For example, by aetivation thrt)«g-h UV irradiation U-Y enhancers may be iheteded in the composition.

Other optional additives melad©,: hat are not limited to viscosity modifiers.

Th ffuorop lymer used ¾ the compositions is preferably present in the ' .form of dispersed particles, for ex mple as a dispersioiif. Typical particle sizes of the rluoropolyrner particles /include from 50 to 500 urn, or from 70 to 359 ' t$vCavef¾ge : particle- stee,/D%*-de*ertinned as Z-average), In one embodimerit, the compositions aj- aijueoys dispersions. Th amount of water east be adjusted: o modify the consistency of the c0st¾pos$t io¾. However, it is also contemplated that water can he replaced by the polymerizable binder material in one embodiment, the composiiions ar pastes, for example

compositions containing ess than 10% by weight of watfeif of sveft ie$$ fcan .§%;.by-¾«¾ight-0-f water-. Sueh pastes are suitable from the paste extrusion process.

The 3D-printable c ntriti n may additionally contain one or more curative whic cures the fiijoroelastomer. The initiator, polymerizabie binder material and curative for the: elastomer are chosen s ' uch that the curatiye is StibstaMiaiiy no activated when the polymerization initiator is initiated,

Siibstantiaily not activated means the euring reactio initiated and/or control led by the curing reaction does not proceed at all or only to an insignificant extent, for example, because the curing reaction proceeds much slower than the polymerization of the binder material. The curati ve is then activated after the object has been created, for example beibre the pol merized binder .material has been removed or

binder material and curing agents/are chosen such that they are activated si different conditions.

In one embodiment a blend of two or more i]uoropo!yn¾ers: is used. Such blends include a blend of two or more lluowpoiymers of the same: type, for example a blend to two or more fluoroeS&sioroer or a blend of elastomers and uon-elastomerie fluoropolytnef's. The fluoropolymers may differ in their chemical eoraposhi^n, by their particle sizes or by combinati ns thereof Msp blends of

T uorothermoplasti:Cs:and iluoroelastotners i»ay he ased

.fe.one embodiment, a 3D printable composition suitable, fo vat polymerization or stereoiithogiaphy comprises:

from .20÷70/¾ wt o one or more fluoroeiastomers;

from 1 to 50¾>, or from 3 to 2S¾ from 10 to 20% . of polytserizahle binder

0 to 1 % of curing agents for curing the f!uoroeiastomer,

0 to..30% by, weight: of filler,- 0 to 10 % of other additives.

and from 10 to 80% of water, (All percentages are pereentby weight and are based ah: ibe total amounto the composition which is 100% by weight).

Wafer is used hi smousts to provide a stable dispsrst fs and the desired viscosity for the printin method, in ease of vatpoiymerization the eom osfti Rs are desirably of low viscosity, fa other processes a h i gher viscosity may be desi red as d no water may be necessary at a) ! . Dispersions: or■solutions are preferred for 3D printing methods like vai-p iymeri ation.

In another eiribbdiment a 3D-printabie composition suitable- ' for vise in paste extrusion methods comprises from 20» 0% w of oiie or more ftuoroelastomefs:

from 3 to 50%, or from 2 to 25% or from 10 to 20%: of po!ymerizahie binder

0 t 10 % of eu itigi geius for curing the lluoroelastoiner,

0 to 30% .b -Wight -of fiber,

0 to i 0 , of - ' other additives,

and f om 0 to 80% of ater * (AJ 1 percentages am percent b weight and are based : on the totai amount of the composition which is 100% ' by weight).

For creating aft -article the3 P-prirttabie composition;: is. -entered into the additive processing machine (3D printer), for example those described for siereo!ithography or paste extrusion and subjected to. additive processing to create s tbree-dimensioital object. The resultin object, also refete to as "green body," m y be obtained br the form of an h d ogel and ma be subjected to drying. It ma be removed f m the 3D printer for that purpose and 5s separated from the un eacted: composition;. The .unreached composition ma be discarded; . or: reused. Prying to remove sol vent or dispersion, mediuat if present Is preferably carried out i ti ,a vyay that av ids the formation of cracks or tilts in the object. Drying should be carried oat in a: manner that the entirety of the green body dries, as ubif rr as; possible to avoid the format! on of cracks o tilts in the object. This can be done ½ a mu! Utud.e of ways. For -example, but not

exterior of the article dries quicker than the interior quick uniform drying in a acuum oven may "foe preferred, for example but not liraited t dr ingiat ?i>0: to i x !9 "3 orr at a temperature between 40 ~ 70 C. in case of larger articles where there is a lot of water present, drying in a humid environment of 50 to 0 % humidity oyer the course of at least 48 hours may be preferred.

The polymerized binder materia! may be removed from the gTeen body, preferabl in a separate beatirfg regime. Cotiyenkntly this: is carried out by hea treatment to degrade (fbr example by oxidization or combustion) and/or evaporate the polymerized material. The temperatures are chosen, such that the i-liioropoiymer article does not melt or gets destroyed. The resulting object may then be subjected to another heat treatment at higher tempet¾£u es. The; eraperatyres are chosen such; that the fluoropoiymer article does not me! tor gets destroyed.

The final artieie iypjcally bas the same shape as the green body, aithOuglf sOrne shrinking:

compared to the green body may be observed, By doing co ' St runs the shri . hfciftg can be taken into

2.1 account when .programming the additive processing machine, Shr . ift . king can be minimised by maximizing the tliioropolyiBer confcniof the !£> printable composition.

The article may e subjected to curing. Curing may be canaed out prior, after or during he removal of the . ' liquid phase, or the removal or degradation of the binder material.

Additive processing by melting or liquefying a binder material

In another embodiment the iluoropolymer article can be created by subjecting defined areas of a 3D printable flueropolymer compositions containin a binder that elts or l iquefies upon exposure to the energy source f the additive processing device id melting or liquefying. In this embodiment the fluoropolymer typically is provided as a Solid composition i form of grannies or as a powder or as extruded fdainents comprising the binder material a i! other additives. The TO printable eouiposition, here comprises at least one binder materia " ! tha reduces its viscosity upon exposure, to the energy source of the isdditsve processing device, for example it me its of lii|uefies upon exposure isthe ienergy source. ofthe : iidditive proeessiiVg machine, whic may be a laser, for example laser of a selective laser melting machine, or if lower tem eratur s can be used the thermal print head of a fhenrial printer, or the heated extrusion head in case of filament deposition printing. Suitable hinder materials, include organic materials, preferably polymers that . ' have, m.eitjfig points above room temperature, preferably above 40°C {but below the degradation temperature of the fii! it>elastomers), .However, polymers that in a strict scientific sense do not melt but soften or become less viscous may also be used. Typieally ¾: the rneitabfc binder has a melting ' point of meite ange within a temperature from about 40 to about 140 C. Organic materials are materials that have c rioh^ b n arid earbon-h dr gen . onds and the : material s ma optionally be :

fluorinafed, i.e. one or more hydrogens may be replaced by fluorine; atoms. Suitable materials include hydrocarbon or hydrocarbon, mixtures and long chain ifydraearhori esters, hydrqearbon alcohols and combinations thereof aftd including their fiuorinated derivatives. An examples of suitable material ih^l-u es.*'a&¾-Sug¾r¾:di ^n5i s thermoplastics haying a melting point as described ato polymerized or cross- linked aerviates, metimcrylates, and -combinations thereof, The w xes may be natural waxes r synthetic waxes. xe are or anic: compounds containin long alky! chains,, for example long chain hydrocarbons, esters of carboxylic acids and long chain alcohols and esters of long chain fatty acids ' and alcohols, sterols and mix ures and combinations thereof Waxes also include mixtures of long chain hydrocarbons. The term ' ong chain'- as-, used herein means a mirn ' mum number of 1.2 carbon atoms. t attir al. waxe include bees ax. A .major epmponeh t of the bees wax i nryrieyl palmitaie which is a n ester of triacontanol and pa!nn ic acid. Spermaceti occurs in large amounts in the head oil of the sperm whale. One of its main constituents is cetyl pahfi itate:. Lanolin is a wax obtained from wool, consisting: of esters of sterols. Garnauba wax is a hard wax containing myrievi cerotate.

Sy betie waxes ihc iude paraffin waxes. These are hydrocarbons, mixture of alkanes usually in. a homologous series of chain lengths. They may include saturated n- and iso- alkanes, naphthylenes, add alkyi- and naphth lehe-substituted aromatic compounds. Also fiuorina ed waxes may be used in whic ease some hydrogen atoms are replaced by fluorine atoms. Ot er suitable axes can be obtained by cracking olyethylen . or pro ylene ("polyethylene wax " or about 50 anil 100. Other examples of suitable waxes: include but are not limited to candelilla wax, oxidized Fischer- ropsch wax, micfocrystalline wax, lanolin, bayberry wax, palm .kernel wax, mutton tallow wax, 3 petroleum derived waxes, mdntan w detivaives, oxidized polyethylene Wax, and combinations thereof.

Suitable sugars include: or^xam ^^ rtrf-i fthQ limMUmj lactose* , trehalose, glucose*, sucrose, ievulbse, dextrose, and combinations hereof.

Suitable dextrins include for exampie and without limitation, gamma-cyelodexrrm, alpha* cycSodextrin,

m eyelodextrim raa!tosyl-beta eyc!odextrm, SAydrOxy-beta-eyci dextrin, 2¾droxypropyl~beta- cyclodexirin, 2 wd x pm

cyclodextrin, sulf butyletbe^alpha-'Cyclodextrirt, su!f buty!elher-beta-cyclodexrrifi, .st iohutyieiher- gamffia-cyciodextiin. and combinations; thereof .

Suitable thermoplastics include for example and without .limitation, i ermopiastk* having a 15 mil ng pomt ofmo greater, than :2O0¾ preferably no greater than 1 such as

po!yethylenererephthaiate (PET), polyiaetie acid (PLA), polyvinyl chloride (PVC) polymethyS methacryjate (PMM ' iA), polypropylene (PP), bisp enol-A polycarbonate (BPA-! ), polys ui tone (PSF), poiyether imide (PEI T . as¾d combinations thereof

Suitable aesylates nd mediaery Sates include for ex le cross-linked or polymerized ser!yates ¾0 meliidiffg ureihan aery!ates, epoxy aerylaies, polyester aeryktes, acrySaied {inefh aefyiics, polye-ther aerylates, aer Sated polyolefins, and. combinations thereoLor t esr ethaeryiate analogs.

Other example of suitable binders incl de but are not limited to binders comprising polymers and polymerized materials selected from, . gelatines, celluloses, e hyl cellulose, hydroxyi ethyl cellulose, hydroxyl p ropy l cellulose , methy l cel lulose, hydroxy propyl cellulose, eel I ulose acetate,

2$ hydroxybutylmethyl cellulose, hydroxyeihyi cellulose, hydroxyethyhheihyi cellulose, glycoses, fructoses, gyicogens, eoUagens, starches, partially fluoriuated thermoplastic r!uoropolymers and combinations

! hereof

Preferably, the mateiiais are of low molecular weight such hat they easi!y degrade at elevated temperatures for example at teroperamres below and including 20 *€ and can be easily removed.

30 The binder material may be present, for exampie, as particles or may he present, for example, as coating on the ftuorOpo!ymer particles. Particie sizes of the binder particies include, for example, from 1 to I SO ,(im (Dot), prefcrabiy about 5 }«a to about SO pm, and mosr preferably about 10 pm to about 30 pm. Ge«eraily, the average particle size of the hinder particles; preferably is larger than that of the i^Oiiopo rtef^telfS j of^mpl ^y^ factor between 2 an 1 0, preferably 2 and 10, The- average

35 particle size of the binder may be ie number averag and ean- be obtained by photographs and particle counting and measuring software.

The optimum: amount, of binder material may be determined by mainly two factors; ΪΪΜ the aHioisni of binder: material hould be high enough such that it allows the -formation of layers: of the desired dimension ' !, i.e. it has to be pfeseift in . an effective ani unt, Secondly, the a oimt stfculd fee ■■ minimised with respect , to the flubropoiymer content to feifiimsse shrinking of the: article- daring the working up

material. Since solid compositions are used, higher fhioropolynler concentrations may be used than in i 1 iquid 3D printable compositions, for example a rluoropolymer contest of up to -90%. b weight or even up to 95 % by weight (based on the weight of the comp¾ ?ti0n) Typieai mou t of binder material meiude but are not limited to amounts from about 5 to about SOv-o, from about 8 to about l $% , for example from about 10 to about 15% by weight based art: the weight of the : total composition,

The compositions may further comprise sol id fillets or pigments, Fifes may include but are not limited t silicon carbide, boro nitride, raoly ' bdenum sulfide, aluminum, oxides, , and carbon particles, stjeh as: grap ite or carbon biacL carbon fibers,, earhoa nanOtubes. The -fiifef .^t^ ' can ¼ ' o &niaedi to the sySteni used and. may typically he between 0,01 to 10 ¾ or up to 30 % weight based on the total weigh! of the composition depending on he fihoropo!ynier and binde materials: lised.

The ilu ropolynier used in the S D-printab!e eempositions of this embodiment are preferably solids and in the form of particles. Typical particle size include particles of from about 1 to 150 (im (¾)- Particle size of solid particles can be determined by microscopy and particle counti g software,

CompositioiiS of stick part icles size can fee obtained by suspension polymerisation of fluoropo!ymers, or by milh ' ng of pellets or billets, of by agglomeration of fluoropoiymer particles obtained from ..emulsion polymerlxa ion, li ens: gm od ' imestj the 3D: printable composition is ia the feon of art extrtidate, for example a fiiameni Such compositions are methods.

The composition ma additi nally comain curatives for curing the fiuoroelastomer. The same curatives may be used: as: d escri bed above w th respect to fee: poly merizablc binder. They are preferably selected: such thai ihe curative is: not activated during the additive processing. The ame elastomers and curatives may be ¾sed as described for the liquid 3 D-pri;niab . ie compositions above,

n one embodiment . a blend :¾f two or more fluoropoiymers: is used. The same blends can be used as described with respect to the poiymerizable binders binders above.

in o e embodiment, the 3 printable composition comprises

from 20 o 95 % -wt or from 70 to 80 ' ■%- . of 8 fluotoefesiomer particles, preferably a. ize between \ and 1 5G pm;

from S to " Cl% or from 5 to 20% of a binder material that melts r iiqaefies at a temperature hetwee n: 40 and T¾0*C, preferably between 50 S G and 10Ο°€, preferably in the form of part icle having: a particle size of from 2pm to 300pra s or from 1 pm to 150 μϊπ,

from 0 to 10 ¾ wt. t of curatives: .tor curing the ' iuOropolymer,

from f) to 50 % wt. Of fillers,

from Θ to 15% t, of ther ingredients wherein the total weight of the composition is i O0S¾.

The solid composition of psrtiele$ or the filament composition ts entered into the additive processing machine (3D printer) providing the appropriate heat source, for example a 3D thermal printer (having a Heat source, such a thermal print heads) or a selective laser wintering .or melting printer having a laser as a heat source, as described : above for selecti ve laser melting, or the ' extrusion heat in ease of TDM, to create a . three-dimensional object. The resulting object, also referred to as "green body " may be removed from the ufireacted powder or filament and subjected to a heat treatment to remove the meltable material Convenientl this is carried out by heat treatment to degrade arid/or evaporate the binder material. The temperatures are chosen such thai the fiuotopolymei- article does not melt or gets destroyed. Such fluorapolymers. articles will retain their shape.. The- heating and subsequent cooling regime may be controlled to avoid bending of the object or formation of cracks in the object. The article may be subjected to eurirjg, preferably after the article has b en created. Curing may fee carried out prior or during the removal of the bi nder material <

Tile resulting object may then he subjected to another heat treatment at higher temperatures. The temperatures are chosen such h i the r aoropolymer article does riot rnelt or gets destroyed.

The final article may R¾ve.Shru»K-to- som ::ex¾nt ' Complied t©: ' ih§:.peen body. By doing control runs, the shrinking can betaken into aeccnini when programming the additive- processin machine.

Shrinking can be mifiittiised by nrajtimizing th finore^

Articles.

Articles of different shapes, designs and functions may be obtained by the. additive processing methods described herein. Such shaped articles include but ace not limited to bearings, tor example feieiiofi bearings or piston bearings, gaskets, shall seals, ringJip seals, washer seals, O-rings, grooved seals, valves an valve seats, conn ctors,: fids, tubing a d containers. The articles obtained by the described processes may be components of other articles. In particular articles of small dimensions may b conveniently produced by the methods described herein, fe one embodimen s^

having at their longest axis or diameter of from about C to about 200 min may be produced.

Flporopolymer articles of big and smal! dimensioas can be produced. The size of the; additive processing device may set; Jimitation to the size .of the artlcjes that c n be produced, Articles: of small dimensions may also be conveniently produced by the methods described herein. An article comprising a 3D-printed tluoroelastomer can be prepared having : a: longest axis (as the ease may be this may also be a diameter) that is smaller than I .0 em or even smaller " than 0.7 mrn. in one embodiment small iluoroelastomer articles may be produced having a longest axis or diameter of from about 1 0.0! to about 1.0 mm, or from 0.7 to 1.5 em , in another embodiment articles may be roduc d,, fo example articles, ffcv ing a smallest axis or diameter of at least 1 ,1 mm.

The rTuotopolyrners can be 3D-printed into articles that have at least one element or part of a defined geometrical shape. Delisted geometrical shapes. include bat are not limited to circles, semicircles, ellipses, half-spheres, squares, rectangles, c bes, polygons (including but not limited to triangles hexagons, pentagons, and octagons) and polyhedrons. The shapes may he three-dimensiona! mi include pyramids, cuboids, cubes, .cylinders, half-cylinders, spheres, ..half-spheres), The sh s: also include shapes composed of different shapes like diamonds (combination of two triangles). For example, a honeycomb structure .contains: several hexagons as .geometrical elements. In one embodiment the geometrical shape has an axis Or diameter of at least 0.5 millimetres,: or at least Me. millimetre; or at least 2 millimetres or at least one centimeter.

in .on : .embodiment of the present disci osure a fJiiOropoiy met a ticle:: is produced contain :ing a D- printed fiuoropolymet that is a "green bo " in. such embodimemVthe article comprises from.3 to 80%. y ' weight of a polymerized binder material, for example a binder Materia! obtained by the polymerization of the polymeri2able bind r material described herein,

in another embodiment of the present disclosure a fluofopolymer aitiele is. produced containing a shaped f fioropoSymer that is a "green body". In such embodiment, the article comprises from i to 25 % by weight of a reaction product of a combustio reaction of l m ria mder material, for example a binder material obtained by the polymerization of the: x>!ymefizable biiider mat&fial described herein,

Fluoropoiymer articles of different shapes, designs and functions may be obtained. Also articles comprising: the fluotepolyiiner artietes of dtfifereni designs and functions may be obtained Examples of artiel s and fluOropo!ymer articles. include but are not limited to bearings, for example: fristion bearings o piston bearings, gaskets, shaft seals, ring lip seals, washer seals. Citings, grooved seals, valves and valve seats, connectors, I ids and containers:. The article may be medical implants, chemical, reactors,: screws, cogwheels,, joints,, bolts, pumps, electrodes, heat exchangers, mixers, turbines, electrical transformers, electrical insulators, static mixers, extruders or the articles may be components, of ther articles including the above articles. The: articles may be used in application where. resistance to acids, bases, fuels, hy c!rdcarbons: i s feqvhre-d, where: non-sii efc : properties are required , where heat resistance is required, a d. combinations thereof..

Preferably, the articles or components thereof contain the im rinted f!uoropalymer wherein the fiuaropob/mer has been 3^ channels, perforations, honeycomb:, structures, essentially hollow structures an combinations thereof; Such structures may be flat, curved or spherical.

List of particul ar embodiments

The folio wing lists of exemplary embodiment is provided to further jllus rate the present disclosure . ■■ without intending to li mit the di sclosure to the speeltle eth bodiments l isted.

L ist i

1. Method of producing, a luoropolymer artie!e!coniprising subjecting a composition comprising flubropolyrner paftieies.to ad iti v processing in an additi ve processing device containing at least one energy source.

2, The method: of embocHjBeni 1 wherein the composition comprises at least one binder material capable of blading the fluoropoiymer particles to form a layer in a part of the composition, that lias been exposed to the energy source of the additive processing-device and the m thod

eomprisess subjee ing a part of th¾-Oomp.<3$itioii to exposure of the Energy, source to Sofi a layer.

The method of an one of the .preceding- embodiments wherein the compositjoiveoraprises at least

com position that has been exposed to the energy source of the - " additive processing device and wherein the binder material is polymeritable and solidifies through polymefi¾ation upon exposure of the compos itidti to the energy source, of the additive processing device and wherein the method comprises subjecting a part of the composition to exposure of the energy source; to form . layer-,

The method of any one of the precedi-ig embodiments wherein the composition comprises at least one hinder materia.! capable of bindin the fluoropolymer particles to form a layer io s part of the composition mat has been exposed to the energy source of the additive processing device and wherein the binder materia! is polymerlza-hle an solidifies through polymerization u on ex osure of the composition to the energ source of the; additive processing de ice: and wherein the mettfod comprises subjecting a part. of the composition to exposure of the energy' source to form, a layer and wherein the .energy source is selected ...from l c roma netic irradiation.

The method of any . one of the preceding embodiments wherein the compos ition compri ses ; at least one binder material eapable of hmding-the iluoropolymer particles to form a layer in a pa of the composition that has : been exposed to the .-energy source of the additive processing device and whereia the binder material ¼ polywerizable and solidifies through polymerization upon exposure of the composition to : ,tbe : energ source of the additive processing de ice arid where in the method cotnpnses subjecting:.a part of the: composition to exposure of the energy source to form a layer and wherein the energ source is electromagnetic irradiation having single or mniti ie wavelengths between 30 nm and ' 1,000. nm.

The method of any one of the p ecedin mbOdiriie ts ' ^herefe the composition comprises at least one binder material capable of binding the iluoropolymer particles o form a, layer in a part of the compos it ion that has, been exposed to the energy source of the add iti v proee ss in device and wherein the binder material is poSynienzaMe arid solidifies through polymerisation upon exp sure of the co osition to the energy source of the additi ve processing device and wherein the method comprises subjecting a part of the composition to exposure of the energy source to form a layer and wherein the energy source com rises ijV irradiation.

The method, of any one of the preceding embodiments wherein the composition comprises at least one binder material, eapahle pf " binding the fluoropolyme particles to orm.* layer in a part of the composition: that h s been exposed to the energy source of the additive processing device and wherein the binder materia! is pQiynierizaWe and solidifies through polymerizatio tipo ' n

the method comprises subjecting ¾ part of the composition to exposure of the energy source io 5 Form a layer and wherein ' the -composition, further comprises at least ' one polymerization initiator

that is initiated by *^po¾yc ½ the. enei¾y -s Hrfce .of ihe -addlfti e process ng device;

8. The method of -my one of the preceding embodiments wherein the binde materia! comprises po!yinerizahie unsaturaied bonds..

io

9. t e method of .any one of the preceding '■ em odiments wherein the binder materia! Comprises polymerizable groups selected: from acryiates and metiiaerylates.

10. The method of any one of the preceding ^ the. binder material comprises

! .5 poiyrrterizable aerylates and ethaery!aies selected from diacryiate, dimetHacrylates,: triaeryiates, ttimeihacry lates, ¾cr I ates .having, four or more aerylste gr0tips > met acrylates havtfig four or mor methaacryl&te rou s: arid combinations thereof.

Π . The method of any one of the precedingiCmbodiments wherein ;the : composition comprises m 0: aqueous dispersion of lluoropofymer particles,

12, The method o any -one of the preceding; embodiments ' wherein the ■■ composition comprises

fluoropo! mer particles haying: a. diameter from about §6 o 500 nm,

13> The method of any One of the preceding embodiments; wiierein the composition comprises

iluoropo!yraer particles having an average particle size .(^-average) of from about $0 to about 500 nm.

14. ' The method of an one of the preceding embodiments wherein the c m ositi n comprises at least one binder material capable of binding uoro olytne particies to form a layer in a part of the composition that has been exposed to the energy source by melting upon exposure; f the composition to . the energy source of the additive ■■ processing, device, and: wherein the method comprises subjecting a rt of†be.;coniposftion to ex osure' of the energy source to form a layer.

I S.. The method of any one of the preceding enrhodimerft wherein the composition comprises at least

composition that has been exposed to the energ source of the additive processing device b melting upon exposure of the composition to the energy: source of the additive processing device and wherein the method comprises subjecting a part of the composition to exposure of the energy source to form a layer and wherein the ener y source of the device is a heat source. 6 ' , The: method of any one of the preceding embod me ts wherein tim : c mposi on com prises at feast one binder material capable of binding tliiGropo!yiser particles to form a layer in a part of the composition diat has been exposed to the energy : . source of the additive processing device, a d \ herein :t e " binder material forms : a layer by meliiftjg: ι οη exposure; of the compos ition to: the energy sourc of the additive processing device and: wherein the additive processing device is a 3D p inter selected from selective laser sintering printers, selective laser melting printers, 30 thermal printer, electron beam melting printer. :·?. he: method of any onei of the preceding embodiments wherein the. composition comprises at least one binder material capable of bifiding fluoropoiymer particles to form a layer In a part of the composition that has been exposed to the energy soarcc of the add iti ve process ing device by melting upon exposure of the composition to the ene gy source of the additive processing device and ; ¾e^m ' tfie ; --met od:-C0iS Hse^-s l¾ecting^ part of the. comrxjskioB to -exposure of the : energy source to form a layer and he ein: the .energy ^^e- ' 0ftbe de i0eis:s.-he^. :S©arce an wherein the binder material has a melting point of at least 40 9 C. 8. The method of any one of the preceding ■embodiments he em the composition comprises at least one binder material: capable of: bindiag fluoropCilymer particles to ' . form a layer in a part of the Composition that has bees exposed to the energ source of the additive processing device- by mel ting upon exposure of the compositio to the energ source of he additke processing device ' and wherein the method comprises subjectin a part of the composition to exposure of the energy source to form, a layer and : wherein the energy source.of the device is a heat sooree and wherein the bi der material . is-.a - wax. 9. The method, of any one of the preceding: .embodiments here in the composition comprises at least one binder mat . eriai capable of binding fiuoropoiymer particles to fortn a layer in a part of the composition that has been, expo ed to the energy source of the additi ve processing device by me tmg. upon exposore of the composition t the energy ou ce of the additive processing-deviee and where i n the method eoinpr i ses su bjec tin part of the com position to exposure of the energy source to form a layer and wherein the energy source- ' of ' the device is a heat source and wherein the composition is solid composition of panicles, 0. The method of any one of the preceding embo iment wherein the .composition comprises at feast one binder material eapabfe of binding fluoropolyrner particles to form a layer in a part of the composition ' tirwi has been exposed to the energy -source of the additive processing device by

20

and wherein "tile method comp ises subjecting a art of Hie eompositiori to xp sure of the energy source - to form a !ayerand wherein the energy soiiree of the device is a heat source and wherein the ffuoropolymer particles have a particle s ze of from, aioot i to about 5 Q uttt, preferably rom about 1 taabqut I SO ίήϊ;

21 . The method of any one of the preceding embodiments wherein the fJuoropolymer is -a

tluoroeiastOmer and wherein, die composition further comprises a curative for curing the flyordeiiiStoris r that is not act! vated during the additive process! og .

22. The method of any one trf the preceding embbdinients iirrthe comprising at least one heat

treatment to remov the binder materia! ,

2 , The method of any one of the preceding embodiments wherein the. c mposition comprises at least on binder material capable of binding fluoropolymer particles to form a layer in an area exposed to the energ source of the additive processing: device and wherein the method further comprises subjeetihg the article to a heat treatraerit td; remov binder material by evaporation.

24, The method of an one of the preceding ernbodiments wherein the composition comprises at leas one binder . materia! capable of binding flaoropolynter particles to form a layer m an area exposed to the: energy source;; of the aiiditiye processing de vice and wherein the. medtod coiri rises stjbjectinglhe: articl to a beat treatment. to. em v binder by thermal degradation.

•25. iuoroeiasiomer article obtained by additive, processing.

26. The: article: of embodiment 25 eoroprising lOm O J to 30·% by weight of otie or more filler,

27. The article of any one:of embodiments 25 to 26 obtainable by the additive processing of any one ■of embodiments I to 24..

28. An artiele comprising a component, wherein the component is a flnoroeiastomer article obtained by additive processing acedrd ing to any one f embod iments 1 to 24.

29.

composition comprisin luorop^lvnier particles, a poiy erizable binde material wherein the polymerizable binder material solidifies upon exposur of t e ^composition to the energy source. 30, The 3D prints bte composition of embodimenl 29, wherein the composition comprises ' a

dispersion of fjyoropoiymer p rties.

3 I , The 3D printable composition of embodiments 29 or 30 wherein the composition further

comprises a poly meri¾a£ ion initiator ' that iiiiitaies polymerization upon exposure to the energy solsrce.

32 S D-printa&le finoropolyme composition for 3D printing using a heat souree, the composition comprising finoropolymer particles and a hinder material that melts upes exposure of the 'composition to the energy .source.

33. The 3D printable composition of em odiment 32, whe drTthe composition is a solid

compos itiom composition comprise fiuoropoly raer part ' teles, a polymerizable binder material and; a pp!ymerixatio initiato thai gets activated by irradiation.

Us : of a iluoropo! mer compositio fo 3 D printing using a hea source, wherein the composition is a so!id compositioii comprising fiaoropoiyrner particles and a binder material that melts upoji ex osure to the beat- source.

List 2

2.1 , Method, of producing a flaompolymer article comprising subjecting■& composition to additive proeessmg in. an one energy source, wherein the . compositio comprises t uoropoiymer particle and a binder materiaS capable of binding the ffnoropplymer partieles t form a layer in a part of the cdrrtposition that ha been exposed to the energy source of the additi ve process ing dev ice and the method comprises subjecting -.a part of the c m o iti n to expositro of the e et¾ source to form a layer and wherein the fi y oropolymer i a BuoroeSastomcr;

2,2 The method according to an one of the preceding embodiments wherein the composition further Comprises, one or more curing agents for can ng the ihiofoelssf orner, and the e hod further comprises subjecting the fluoroelasi nier to curing.

2.3, The iSethod according to any one. of the preceding: esnb diments further earapf is ing remov ing the - ' binder material 2.4. I e njef hod according to any one of the preeeding: em odiments wherein th

f!uomelasiottTer Gompfi&es repeating units derived from- tetratTuorocthene- arid one or more

peril uoraaie alpha olefin ethers eprr&s> Oi¾ i;Rg. to the for-mata

wherein n represents 1 qr-0 and R s ' represents a.linear or branched, cyclie or acyclic pertluorinated alky! residue optionally Being . interrupted once or more than osiee by an oxygen atom an R f preiem ly aving less than 12 e¾ bon atoms, trio s prefe ably having up to ? carbon; atoms. 2,5. The method . according te - any one of the preceding embodinients hereii the llu roelastomer has a glass transition temperature (T u; ) of less than 25*€«

2.6. The method according to any one of th preced ing embodiments: wherein the binder material is po!ymeri abls, and binds fiuoropoiyt.her particles by polymerizing upon exposure to the energy source.

2.7. The method according to any one of the preceding embodiments- wherein the binder material is oSymerKabie and binds Mioropo!yraer: particles by polymerizing upon exposure to the: energ source eoiriprises and wherein the binder material comprises polyrnerizable;

unsaturated bonds.

2.8. The. method according to any one of the preceding embodiments, wherein ½ composition is a dispersion of the fluoroelastomer particles in a fluid phase.

2.9. The method according to any one of the preceding embodiments wherein the binder materia! is pofytnenzable and comprises polym.enzafcie groups selected from aery late and meth aery late groups.

2.10. The 'method according to any one of the preceding embodiments wherein the binde material is polymeriiiabieyan . binds flnoropoiymer partieies by polymerizing upo exposure to the energy source an wherem the conipositlon is a. dispersion, f the fiitoroelastomer in a fluid phase and wherein the poiymerizable binder comprises polyrnerizable groups selected from silane groups. 2. ί I . The method according to an one of the preceding embodiments wherei the binder material is polymerizable, and binds flttoropoiymer particles by polymerizing upon ex osure to the energy source and wherein the com posi t ion , is? ft extendabl compositio .

2.1 , The Method aeePrdiPg vto my ' one? of the preceding embodiments? whfeiiei th binder material is polymenzable, and binds fluoropoiymer particles .fey polymerizing upon exposure to the energy source and wherein the composition is an ejih i ' ikbJ composition and wherein the po!yfnerizable binder com ises poiymemabie groups se!eeted from aeryiate an : d::met;haerylate :gronps.

2,13» ' Jm- ia& bd. a^.o in¾- 1& ¾j*V. one of the preceding embodim nts wherein he method comprises the steps:

(i) providing the composition containing the fSnorOpolymer particles and the binder material and optionally other ingredients and wherein the binder material is po!yroerizable, and binds finorop¾iy er particles by polymerizing: upon .exposure , to the energ source;

( i) cansing the, binder material io : polymerize a d to bind f!apropolymer particles by either (a): directing energ fro : the energy source of the additive man«i¾ett.ring device to a selected location of the 3D printable composition and causing the binder material to polymerize and to bind fluoropoiymer pan icles in the selected location- or(b¾: : directing a selected location of the 3 D printable composition to the energy source and causing the binder rn&terial ?to polymerize and to bind fiaoropoiyniei" particles, or a eom ination of (a) and (b) .

(iii) directing either (e) the. energy source away from the 3D printable Composition or id) directing the 3D printable composition away from th energy source or both, to avoid the binder material polymerizing: in the no«»seIected. locations, or a combination of (c) and (d);

(iv) repeating stfeps (is) and (iii), and If heees¾ry also step {|}; to fbrr{. multiple -layers and c eate an article

2, 1.4. Th method according to an one of the preceding embodiments wherein the binder material melts or liquefies upon exposure to the energy source and binds the fluoropoiymer particles,

2.13 , The method according to any one of the preceding embodiments wherein the binder material melts or liquefies upon exposure to the energy s urce aisd binds the fluoropoiymer particles and comprises or anic: particles selected from w x, sugars, dextrins, and thermoplastic polymers raeitin betweefi 4 ¾ G nd 180 °C,. polyethylene gl cols, melting fetweeil4Q% and 1 M a C and polymerized or cross^ linked ae^¾ sj-m- th.«cr ' teies;¾i.!d combinations thereof

2.1,6, The method according to- " my .on ..of the preceding embodiments whepetft the binder material me its "of liquefie up n 1 exposure to the: energ source arid binds ' the fluoropo!yrBer particles a ' bd wherein the composition is a solid composition of particles.

2.17. The , method ..according to any ^nfc : 0f tfte ' ppgec! lng . ¾ra ' bc^tee«is. wherein the binder material melts or liquefies: upon exposure to the energy source and binds the iluoropidymer particles and wherein the composition; has been extruded into a: filament.

2, i H. The method according to any one of the preceding em bodisnenis wherein the binder material melts or liquefies upon exposu e to the ".energy source and binds the fiuoropolymer particles and wherein the composition has been extruded into a filament * and wherein in the energy source comprises a heated extrusion nozde. through which the composition is extruded,

2, 1 The method according to any one of the preceding: embodiments wherein the method comprises: the: steps:

( ) providing th composition containing the flnoropolymer pafitiel.es and the binder materia! and optionally other ingredients and: wherejn the bifider material melts or l iquefies upon exposure to the energy source and binds the tfeoro olyraer particles;

( ii ) eausmg the binder material to melt or liquefy and to bind fiuordjxdymer particles b either Ca); directing energy from th energ source of the additive m ni!&etu m device to a selected . location Of th 3D printiible cQmpositi ft and causing the binder material to melt or liquefy arid to bind fluorepofymer particles i n the: selec ted locat ion;, or (b : direct ing a selec ted location of the 3 D printable : composition to the energy source and eausingihe binder material to melt or Hqnely arid to bind fluoropoiy er particles, or a .combination of (a) and (b);

{ s i i ) directing: e ither ' (¾) the energy source away from the D printable composition: or d) directing the 3D : pri.ntab:le composition away from the energ source both. iO avoid the binder materia! to ffielt or liquefy and to bind fluoropoiymer particles in the non -selected locations, or a combination of {ø) and (d);

(iv) repeating steps i:ii),an : .(¾.), and if necessary also st p: (i), to form multiple layers an c eate an article,

2,20:, A composition for producing ah articl by additive processing in an additive processing device, said composition comprising. fluoropotyiner particles, optionally one or more filler, arid a binder materia! capable of la di the flaord oiyifter particles upon exposure of t binder material to energy from an energy source of the additive processing device;■wher in th fiuoropolymer is a ihtoroelasiomer.

2.21 , The composition of embodiment 2.20 wherein the fluoroeiastomer comprises repeating units derived #onr tet £iftuoroediene and one or more comohomers selected from:

nexafiyoro ropene, v nyiidene fluoride and one: r m re pgrfftiorinated: alpha olefin ©iters corresponding to the formula

wherein ¾ re resents-' 1 or 0 and ft* represents, a .J mear or branched, cyclic: or aeyeS ic perfliiorinated aikyl residue optionally: feeing interrupted once of more than nce by an oxygen atom and R 1 preferabl haying iess than 12 carbon atoms, more preferably . having up .to 7 carbon atqrss.

2 ,22. The composition of embed imem 2.20 or 2. 1 w here in the 11 uoroe las ome r has a glass transition temperatsire (Tg) of less han 25*0.

2.23. e composition of embodiments 2.20 to 2,2:2 wherein the .fluoropolynier particles have an average parti cle: size ¾) of I om SO to 50.0. n ,

2.24. The composition of ' embodiments 2.20: to 2.2.3 further comprising one or more curing agent for curing th f eoiOelastoraer.

2.25. The composition of embodiments 2.20 to 2.24 being a dispersion of fluoropolymer particles in a liquid phase and hsrein the

polymer izahtevgrowps . se leered from acrylate and m ethaer y late grou s .

2.26. te COm si iim of embodiments 2 ,20 to 2.2-5 wherein the eoniposiyon is an extmdabie composition.

2.27. The: composition of embodiments 2&§W%2£ wherein ine binder material melts or l quefies, upon ex osure to the energy source and comprises organic paitteies selected from wax, sugars, dextrirts, and thermoplastic polymers -melting between 40°€ and 180 °C

2..2S. he composition of embodiments 2.20 to 2,27 wherein the binder materia! melts or liquefies..upon exposure to the energy; source wherein the composition is a solid composition of particles, 2,29:. ' The compijslisoii of em odifSients 2.20 to 2;.2S wherein the bmder maiorial melts or liquefies upon exposure to She energy source aiid comprises organic particles selected from wax, sugars, dextr s, md thermoplastic polyiriers rtnelttsg between 0°€ and 80 °0 an wherein the 5 composition is a solid composition.

2.30 A comppsititM comprising a 3D- riotM flaofoeiastonie .

2.3 1. The composition of emlx>dii¾erit 2,30 being obtainable by the method of any one of i 0 e mhodi en ts 2, 1 to 2.19 in ' c lusi ve:

2,32, An article comprising the D^pnnted fiiW^Jastom^r^i ' ^b d ' im^Sit ' S^i ' H ' 2.3 I, the: article being selected front friction bearings, piston bearings, .gaskets, shaft seals, ring lip seals, washer seals, ( irigs s ' valve seats;* connectors ' aiid lids,

15

The disclosure ' will now ' e farther illustrated by examples and test method without intending the diseiosu re So be limited to : the- tests and exantples below .

Test Procedures

Average- Partle!s: "Size:

Average particle s ze of polyme -particles in a dispersion can be: measured by electronic light scattering using a Malvern Autosszer 2e in accordance ith ISO 1 321. This method assumes a spherical particle size. The average particte ste

Wherein Si is the scattered intensity of partic le i and D, is the diameter of particl e I Th is equat ion typically corresponds to the -.equation;

DZ = =-~r in the diameter range of the particles used herein. The particle si zes are expressed as the Dm value.

Solid Cani ru:

according to ISO ί 2086. A correetioo.for nonvolatile inorganic salts was net carried out. Glcim tmiiiiim (emperaiwe fig):

The Tg can be measured by differential seanniiTg ca rimetry, for example using aTA

itistraffieiits Q200 modulated DS^Conditionsof measurements;: heating rate from ^IS0°C to S0°Cai 2- 3°C / minute.. The jnoduiaticm amplitude; !¾per minute dnmg 60 seconds,

Moo ey viscosity;

oorie iscosities can be detemniBed In accordance with AST D ί 646 - 07(2012),

S nimute re-heat nd a 10 , .min-ut«: test: at !2i :> C {ML !÷10@ iSI^C).

Examples.! i&

Prepiirtioii of PFE V eursfrle dmpermms

f)g of an at eo s dispersion comprising a p« : r uoroeiast0mer (TFE-PIVWE cQpofymer conlaiiJing; mirite .groups as cuf ing sites; PFE 19.1 TL2, -27 % solid ettfttetit * . obtained from .Dyrseon GmbH, jBufgkirehen, Germany) was added into a 60 mL■ -amber glass jar unde magnetically stirring at 400-500 rpm. A pre-mixed solutior? rof binder material SR-344 (3.0 g), SE-41 ' 5 (S.Og) (both from Sartoffier USA, LLC (Exton, PA 19341), arid 1RG AG LIRE.2022 (QMS g, from BASF Cop ation (Wyandotte, Ml 48 i j) »is dropwse added sirto tl¾e peril uoroelastonier dispersion and stirred until it became homogenous. T he dispersions were allowed to sitover nigh .before us .

For additional C &ig ' agents, either lisxarotee 0.50 g) or CEJOG? !¾ Fi¾ : R.0CQG¾ (0.40 g was dissolved into previoiis PFE dispersions..- The final solutions were translucent,;

The solutions were used to produce s ets , .by additiv iiMtiuaeturin (VAT polymerization:). Additive raahufaetining was carried out in a eoawierciai!y available desktop 30 printer, Asig PICO 2 (a high power LED g385 nm as the UV soaree). After printing, the.gel saffiples : ei¾ carefully detached with aMr blade from she aluminum platform. The samples were dried under air and then under vac um to remove water.

They were further treated: at different temperature for ring and removing binder.

The freshly ID-printed PFE sheets were -typically transkeent and fragile. due tetwaief remaining inside the sheets, They had a dimension of apprdxi iateiy 47 x 30 x 2,5 mm (1 % w x K), After a first heating step (drying

the sheets- were diy and turned .½. The :sheets had a dimension: of a oat,3 . x 22 x 1.7 mm (1 x w x li). The sheets had a ge.l-like i: . rubbery consistency. After a: second eat treatme«t . (2 0°C for 2 hours), the sheets turned brown and .became sliffet. The dimensions ereabout 3 J x 2Q.x 1.5 mm. After a sec nd heat treatment (350 £ 'C for 72 hours) the sheets become harder. The dimensions were approximately about 25 χ ½.:x 1.ft ne determined using a ruler.

The samples ere : : analyzed before nd after the different heating stages by ATR-1H. Attenuated Total Reflectance (ATR) is a technique by which an infrared (IR) spectrum of a surface is measured. The samples were pressed onto an IR-transpareut crystal usin -.subs antial pressure to ensure imii% contact between the crystal and sample swrface, FJuHng analysis, an IR beam is t fie$se& jfi¾m ' the- "mn&t suri¾ofe of the crystal, such that it penetrates the sample with a depth of a .fe microfis or less, Each sample wg$ cut fey a. razor blade. Th« freshly cut surfaces of samples e¾ placed on Ge crystal window to collect the spectrum, ATR- IR spectra with 4 cm'' resolution were acqu red from a Pike Sroatttvf IRaeie ATR accessory with a sifigle-reflee-tion horizontal genwahium (Ge) crystal. The aoeessofy was inserted into the sample compartment of an. iS50 FTIR s ectf^nseter fetm Thermo " piicote with :¾. room-femperat«re KBr-DTGS diiteeior. Each spectrum was acquired with 32 scans and a speetrai range of 600 ^ 650 cm" 1 .

AH .ATR-IR spectra of the freshly prepared 3D-printed sheets showed small peaks at 2262 cm "! indicating the nitrile (~C ) curing sites from PFE fluoroelastonier backbone . Because of the low concentration of the nitrite fireetionaiity in the total m sSj the intensity -o the signal was ' .small. The sharp peaks at 1735 cstf f were the chameterisiic pea¾s of earbon l groups (€~Q) frtfrii acrylate binder (SR-344 and Sf fS),

After the heat-treatment at 209 °C overnight, the ATR- iR spectra showed that the sample made front Example #1 till had the peak attributed to the - N curing sites (2262 cm '1 )- Samples made from Example #2- (with curing additive hes¾mine) arid. Example #3 (with cutting additive CFj©Cjf¾OGF:(GF?3C0ON¾) had : no detectable" signal at 226 em- . This is an indication that cross!iriking of the ferfluaroeiastomef s occurred.

Under the same conditions, the persistence of 1725 em "' peaks from alt the samples is an indication that aery!ate binder molecule were still present,

ATR-IR spectra of the samples wore: . subsequentl treated - t 350 9 for 7 ks before cooling to room temperature showed, no ' G i= 0 peaks , any ore, except for the sample from experiment 1 but the peak was verv small. This indicates that aerviate binders degraded under this. heat treatment.