Patent Application
20200189181
Fused filament fabrication (“FFF”), also known as fused deposition modeling, is an additive manufacturing technique wherein the FFF printer deposits layer over layer of a thermoplastics build material to create a 3D model. During printing, each new layer must be supported by the layer beneath it. If the model to be printed requires support, such as for such as an overhang or bridge, to maintain its desired shape, the printing of support structures may be needed to support the model until the model cools sufficiently to maintain its structure.
In the FFF process, the build material and support material, as feedstock, are fed to the FFF printer in filament form. These build and support material filaments are then separately heated to liquefy each and then to extrude them through separate nozzles to enable the printing of the model and support structures.
The support structure is subsequently removed from the completed model by physical separation, dissolution, or a combination of the two.
An ideal support material must satisfy many different and sometimes contradictory requirements, including the ability to be readily extruded to form a high-precision filament, the ability to be printed to form a support structure, and an affinity for the build material that is sufficient to enable support of the build material during printing but not so great as to interfere with removal of the support structure from the final model or to damage it during removal of the support structure from the model.
To print using a build material, with a high heat resistance, such as a polyetherimide resins, elevated printing temperatures are required to print these build materials. When printing with these high heat resistant build materials, the support material must also be sufficiently resistant to these elevated temperatures to maintain enough stiffness to provide structural support to the build material. There remains a need for heat resistant support materials exhibiting an improved balance of these properties.
One embodiment is an article of manufacture comprising a filament for use in 3D printing wherein the filament comprises (a) 95.5 to 99.5 weight percent of an amorphous, thermoplastic resin, having a Tg from 165° C. to 350° C., and (b) 0.5 to 4.5 weight percent of a high viscosity silicone, having a kinematic viscosity from 60,000 to 100 million centistokes at 25° C. (hereinafter “cSt”), based upon the combined weight of the thermoplastic resin and silicone in the filament, and wherein the silicone is immiscible with the thermoplastic resin.
Another embodiment is an article of manufacture comprising (a) a support structure which comprises (i) 95.5 to 99.5 weight percent of an amorphous, high heat thermoplastic resin, having a Tg from 165° C. to 350° C., and (ii) 0.5 to 4.5 weight percent of a high viscosity silicone, having a kinematic viscosity from 60,000 to 100 million cSt, and (b) a three dimensional model which comprises a second thermoplastic resin wherein the second thermoplastic resin and the high heat resin are not the same, and wherein at least a portion of a surface of the support structure is adhered to at least a portion of a surface of the three dimensional model.
Yet another embodiment is a method of fused filament fabrication comprising: melting a portion of a first filament to form a first thermally-solidifiable material in molten form, and dispensing the first thermally-solidifiable material in molten form in a predetermined pattern so as to define a three-dimensional object; and melting a portion of a second filament to form a second thermally-solidifiable material in molten form, and, in coordination with the dispensing the first thermally solidifiable material, dispensing the second thermally-solidifiable material in molten form so as to define a support structure for the three-dimensional object; wherein the second thermally-solidifiable material comprises (a) 95.5 to 99.5 weight percent of an amorphous, high heat thermoplastic resin, having a Tg from 165° C. to 350° C., and (b) 0.5 to 4.5 weight percent of a high viscosity silicone, having a kinematic viscosity from 60,000 to 100 million cSt, based upon the combined weight of the thermoplastic resin and silicone in the filament, and wherein the silicone is immiscible with the thermoplastic resin.
These and other embodiments are described in detail below.
The terms, as used herein, have the following meanings.
The terms “a” or “an” means one or more.
The carbon atom content of the various hydrocarbon-containing moieties herein may be indicated by a prefix designating the minimum and maximum number of carbon atoms in the moiety, for example, the prefixes (Ca-Cb)alkyl, and Ca-b-alkyl, indicate an alkyl moiety of the integer “a” to “b” carbon atoms, inclusive. Thus, for example, (C1-C6)alkyl and C1-6alkyl refer to an alkyl group of one to six carbon atoms inclusive.
A substituent, as defined herein, is an atom or group, which is bound to the parent chain of a thermoplastic resin or silicone. The substituent may be monovalent or divalent.
A bridging group, spacer, linker or diyl group is any part of a molecule or polymer repeating unit with formula connected by single bonds to two other distinct atoms in the rest of the molecule or repeating unit.
The term “alkyl” denotes a straight or branched aliphatic, saturated or unsaturated, monovalent substituent. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, vinyl, allyl, 2-methylpropenyl, 2-butenyl, 1,3-butadienyl, ethynyl, propargyl, and the like.
As used herein, the term “hydrocarbyl”, whether used by itself, or as a prefix, suffix, or fragment of another term, refers to a residue that contains only carbon and hydrogen. The residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can also contain combinations of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties. However, when the hydrocarbyl residue is described as substituted, it may, optionally, contain heteroatoms over and above the carbon and hydrogen members of the substituent residue. Thus, when specifically described as substituted, the hydrocarbyl residue can also contain one or more carbonyl groups, amino groups, hydroxyl groups, or the like, or it can contain heteroatoms within the backbone of the hydrocarbyl residue.
The term “alkanediyl” means a divalent aliphatic radical, saturated or unsaturated, bridging group having from 1 to 10 carbon atoms, such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, and isomeric forms thereof.
The term “aryl” denotes a monocyclic or polycyclic aromatic hydrocarbon group, for example, anthracenyl, fluorenyl, naphthyl, phenanthrenyl, phenyl, and the like.
The term “arylene” means a diradical obtained by removing two nuclear hydrogen atoms from a monocyclic or polycyclic aromatic hydrocarbon groups. Illustrative of arylene are phenylene, tolylene, xylylene, naphthylene, diphenylylene.
The term “cycloalkylene” means a monocyclic or polyclic, cycloaliphatic, saturated or unsaturated, divalent radical such as 1,3-cyclobutylene, 1,3-cyclopentylene, 2-methyl-1,3-cyclopentylene, 2-ethyl-1,3-cyclopentylene, 1,4-cyclohexylene, 2-methyl-1,4-cyclohexylene, 1,3-cycloheptylene, 1,4-cycloheptylene, 5-methyl-1,3-cycloheptylene, 1,3-cyclooctylene, 5-methyl-1,3-cyclooctylene, 1,4-cyclooctylene, and the like.
“Cycloalkylidene” means a monocyclic or polyclic, saturated or unsaturated, cycloalkyl group linked to the remainder of the molecule via a double bond. The definitions and illustrations provided herein for cycloalkyl groups apply with appropriate modification also to cycloalkylidene groups.
The term “alkoxy” refers to straight or branched, monovalent, saturated or unsaturated aliphatic chains of carbon atoms bonded to an oxygen atom that is attached to a core structure. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, iso-butoxy, and the like.
The term “cycloalkyl” denotes a saturated or unsaturated monocyclic or polyclic cycloalkyl group. Cycloalkyl groups may be optionally fused to aromatic hydrocarbons such as benzene to form fused cycloalkyl groups, such as indanyl and the like. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like.
The term “halogen” or “halo” represents chloro, bromo, fluoro, and iodo atoms and substituents.
The term “melt”, as used herein means to heat an amorphous polymer above its glass transition temperature or, for a crystalline polymer, to heat to cause a phase change from the solid phase to a liquid phase.
A repeating unit or unit means a part of a polymer whose repetition, by itself or with other repeat units in a copolymer, would produce the complete polymer chain (except for the end-groups) by linking the repeat units together successively along the chain.
The term “substituted” means that a hydrogen atom on a molecule has been replaced with a different atom or molecule. The atom or molecule replacing the hydrogen atom is denoted as a substituent.
The present inventors have determined that support filaments and materials described herein are useful to support the 3D printing of heat resistant model materials, such as polyetherimide, and are more readily separable from the printed models than are presently available support materials.
In one embodiment, the article of the present invention comprises a filament useful for forming a support structure for 3D printing. Typically, the filament has an average diameter from 1 to 5 millimeters with a standard deviation of ±0.1 millimeters.
This filament comprises 95.5 to 99.5 weight percent of an amorphous, high heat thermoplastic resin, having a Tg from 165° C. to 350° C., and 0.5 to 4.5 weight percent of a high viscosity silicone, having a kinematic viscosity from 60,000 to 100 million centistokes, based upon the combined weight of the thermoplastic resin and silicone in the filament.
The composition of the filament of the present invention comprises (a) 95.5 to 99.5 weight percent of an amorphous, thermoplastic resin, having a Tg from 165° C. to 350° C. Examples of suitable amorphous, thermoplastic resins include, but are not limited to, polypenylene ethers, polyetherimides, polyamideimides, polyetherimidesulfones, polysulfones and copolycarbonates.
In one embodiment of the composition of the filament, the amorphous, thermoplastics resin is a polyphenylene ether homopolymer (“PPE”) comprising repeating structural units having the structure of formula (1a), as follows,
wherein each occurrence of Z1 is independently halogen, unsubstituted or substituted C1-C12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, hydrocarbylthio, C1-C12 hydrocarbyloxy, or C2-C12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and each occurrence of Z2 is independently hydrogen, halogen, unsubstituted or substituted C1-C12hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, hydrocarbylthio, C1-C12 hydrocarbyloxy, or C2-C12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms. In some embodiments, the phenylene ether units comprise 2,6-dimethyl-1,4-phenylene ether units. The poly(phenylene ether can further comprise molecules having aminoalkyl-containing end groups and tetramethyldiphenoquinone end groups. The poly(phenylene ether) can be in the form of a homopolymer, a copolymer, a graft copolymer, an ionomer, or a block copolymer, as well as combinations thereof.
In other embodiments, the poly(phenylene ether) comprises a poly(phenylene ether)-polysiloxane block copolymer (“PPE-Si”). As used herein, the term PPE-Si refers to a block copolymer comprising at least one poly(phenylene ether) block, of formula (1a) above, and at least one polysiloxane block of formula (1b) below. The at least one polysiloxane block comprises siloxane units having the structure of formula (1b), shown below,
wherein each occurrence of R4 is independently C1-C12 hydrocarbyl. In some embodiments, each occurrence of R4 is methyl. In some embodiments, the phenylene ether units comprise 2,6-dimethyl-1,4-phenylene ether units. Also, in some embodiments, the PPE-Si may be hydroxyaryl-terminated.
It is not necessary to separate the PPE from the PPE-Si. The PPE-Si can thus be utilized as a “reaction product” that includes both PPE and PPE-Si. Methods for the preparation of PPE-Si include those described in U.S. Pat. Nos. 8,017,697 and 8,669,332 to Carrillo et al.
In another embodiment, polyphenylene ethers include a blend of a polystyrene, such as general purpose polystyrene or high impact polystyrene, with PPE, PPE-Si or a blend of PPE and PPE-Si. The polystyrene-containing blend may contain up to 30 weight percent polystyrene.
In the embodiment of the composition of the filament wherein the amorphous, thermoplastic resin comprises a polyetherimide, the polyetherimide can be selected from polyetherimide homopolymers, polyetherimide co-polymers such as with siloxane or sulfone, and combinations thereof, and blends with polycarbonate.
In one embodiment, the polyetherimide is a polymer comprising etherimide units of formula (2a), shown below,
wherein T is —O— or a group of the Formula —O—Z—O— wherein the divalent bonds of the —O— or the —O—Z—O— group are in the 3,3′,3,4′,4,3′, or the 4,4′ positions of the phthalimide groups; Z includes divalent moieties of the formula
wherein Q is a divalent moiety that can be —O—, —S—, —C(O)—, —SO2—, —SO—, —CyH2y- wherein y is 1 to 8, or —CpHqFr— wherein p is 1 to 8 and q is 0 to 15 and r is 1 to 16 and q+r=2p; and R2 is independently at each occurrence a divalent group selected from the group consisting of substituted or unsubstituted divalent aromatic hydrocarbon moieties having 6 to 20 carbons, straight or branched chain alkylene moieties having 2 to 20 carbons, cycloalkylene moieties having 3 to 20 carbon atoms, and divalent moieties of the general formula (2b)
wherein Q is defined above. In this context, “substituted” means including at least one substituent such as a halogen (i.e., F, Cl, Br, I), hydroxyl, amino, thiol, carboxyl, carboxylate, amide, nitrile, sulfide, disulfide, nitro, C1-C18 alkyl, C1-C18 alkoxyl, C6-C18 aryl, C6-C18 aryloxyl, C7-C18 alkylaryl, or C7-C18alkylaryloxyl.
In some embodiments, each occurrence of R2 is independentlypara-phenylene or meta-phenylene, and T is a group of the Formula —O—Z—O— wherein Z is a divalent moiety of the formula
Methods of forming such polyetherimides are described in U.S. Pat. No. 4,910,288 by Brent A. Dellacoletta.
In another embodiment, the polyetherimide is a copolymer of etherimide units of formula (2a) and siloxane units of formula (1b). Methods of forming such copolymers are described, for example, in U.S. Pat. No.: 7,847,023 by Robert Russell Gallucci et al., U.S. Pat. No. 4,404,350 by Hong-Son Ryang, U.S. Pat. Nos. 4,808,686 and 4,690,997 by James A. Cella et al., and U.S. Pat. No. 8,013,251 by Yashpal Bhandari et al. In one embodiment, the polyetherimide is a polyetherimide-polysiloxane block copolymer, commercially available from SABIC as SILTEM™ resin.
In the embodiment wherein the polyetherimide is a polyetherimide sulfone co-polymer, the copolymer may be made from the reaction of a dianhydride and a diamine. Exemplary dianhydrides have the formula (2c)
wherein V is a tetravalent linker selected from the group consisting of substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic groups having 5 to 50 carbon atoms, substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms and combinations comprising at least one of the foregoing linkers. Suitable substitutions and/or linkers include, but are not limited to, carbocyclic groups, aryl groups, ethers, sulfones, sulfides amides, esters, and combinations comprising at least one of the foregoing. Useful diamines include diamino diaryl sulfones and combinations thereof. Diamino diaryl sulfones (DAS) have the general formula (2d):
H2N—Ar1—SO2—Ar2—NH2 (2d)
wherein Ar1 and Ar2 independently are an aryl group containing a single or multiple rings. Several aryl rings may be linked together, for example through ether linkages, sulfone linkages or more than one sulfone linkages. The aryl rings may also be fused. In one embodiment Ar1 and Ar2 independently comprise 5 to 12 carbons. Methods of forming such polyetherimide sulfones are described in U.S. Pat. No. 9,909,006 by Hariharan Ramalingam et al. In an embodiment the polyetherimide sulfone comprises structural units having the formula (2e)
In another embodiment, the polyetherimide is the reaction product of Bisphenol A dianhydride with 4,4′-diaminodiphenylsulfone. Such a polyetherimide sulfone is commercially available from SABIC as an EXTEM™ resin.
In a further embodiment, the polyetherimide is a blend of polyetherimide homopolymer and polycarbonate which is available from SABIC as an ULTEM™ 9085 resin.
In the embodiment of the composition of the filament wherein the amorphous, thermoplastic resin is a polyamide-imide, the polyamide-imide may be a homopolymer or a copolymer. In another embodiment, the polyamide-imide is as disclosed in U.S. Pat. No. 3,554,984 by Norman George and U.S. Pat. No. 3,658,773 by Wilfried Zecher. In another embodiment, the polyamide-imide comprises one of the following monomers:
In yet another embodiment, the polyamide-imide includes the following formulation.
In some embodiments wherein the amorphous, thermoplastic resin comprises a polysulfone, the polymer includes a repeat unit comprising a divalent aryl ether group and a divalent sulfone group such as in polysulfones (PSU), polyethersulfones (PES), and polyphenylsulfones (PPSU) and poly(biphenyletherdisulfone).
In one embodiment of the composition of the filament, the amorphous, thermoplastics resin is a high heat polycarbonate. As used herein, a high heat polycarbonate comprises a high heat copolycarbonate, a high heat polycarbonate homopolymer, or a mixture thereof. A high heat polycarbonate homopolymer comprises a high heat carbonate unit while a high heat copolycarbonate comprises one or more different high heat carbonate units and, optionally a Bisphenol A carbonate unit shown below.
Optionally, the high heat polycarbonate further comprises a Bisphenol A polycarbonate which may be a linear polycarbonate, a branched polycarbonate or a linear polycarbonate and a branched polycarbonate.
The term “polycarbonate” and “polycarbonate resin” refers to polymers having repeating units of the formula —C(O)—O—R100—O— (hereinafter “formula (3a)”) wherein each R100 may independently comprise any suitable organic group, such as an aliphatic, alicyclic, or aromatic group, or any combination thereof. In certain embodiments, R100 may be a C6-C24 aromatic group wherein at least one moiety is aromatic. The polycarbonate may include repeating units of the formula —C(O)—O-A-Y-A-O— (hereinafter “formula (3b”) wherein each A is a monocyclic divalent aryl group and each A can be the same or different. Y is a bridging group having one or two atoms that separate each A such as O, S, S(0), S(0)2, C(O), methylene, cyclohexyl-methylene, 2-[2.2.1]-bicycloheptylidene, ethylidene, isopropylidene, neopentylidene, cyclohexylidene, cyclopentadecyclidene, cyclododecylidene, and adamantylidene. The repeating units of formula (1) may be derived from dihydroxy compounds as described in WO2015160957.
In another embodiment, the high heat polycarbonate comprises high heat carbonate units and other types of polymer units such as polysiloxane units, and combinations thereof.
In one embodiment suitable high carbonate units include phthalimidine carbonate units of formula (3a)
wherein Ra and Rb are each independently a C1-12 alkyl, C3-8 cycloalkyl, or C1-12 alkoxy, each R3 is independently a C1-6 alkyl, R4 is hydrogen, C1-6 or C2-6 alkyl or phenyl optionally substituted with 1 to 5 C1-6 alkyl groups, and p and q are each independently 0 to 4, or 0 to 1. In another embodiment, Ra and Rb are each independently C1-3 alkyl, each R3 is independently C1-4 alkyl, R4 is hydrogen or phenyl optionally substituted with up to five C1-6 alkyl, and p and q are each independently 0 or 1.
In an embodiment wherein R4 is phenyl, carbonate units can be derived from 2-phenyl-3,3′-bis(4-hydroxy phenyl)phthalimidine (also known as 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one or N-phenyl phenolphthalein or “PPPBP”). In another embodiment, where R5 is methyl, carbonate units can be derived from 2-methyl-3,3′-bis(4-hydroxy phenyl)phthalimidine (also known as 3,3-bis(4-hydroxyphenyl)-2-methylisoindolin-1-one or N-methyl phenolphthalein or “MPP”).
In another embodiment, suitable high heat carbonate units can have any of the following formulas
wherein Rc and Rd are each independently C1-12 alkyl, C3-8 cycloalkyl, or C1-12 alkoxy, each R6 is independently C1-3 alkyl or phenyl, preferably methyl, Xa is a C6-12 aryl, C3-18 cycloalkylene, C3-18 cycloalkylidene, -(Q1)x-G-(Q2)y-group wherein Q1 and Q2 are each independently a C1-3 alkanediyl, G is a C3-10 cycloalkylene, x is 0 or 1, and y is 1, or —C(P1)(P2)— wherein P1 is C1-12 alkyl or C6-12 aryl and P2 is C6-12 aryl; and m and n are each independently 0 to 4, or 0 or 1.
In a further embodiment, exemplary high heat carbonate units include:
wherein Rc and Rd are the same as defined herein for formulas (3d) to (3h), each R1 is independently hydrogen or C1-4 alkyl, each R2 is independently C1-4 alkyl, and g is 0 to 10. Preferably, each R1 is independently hydrogen or methyl, each R2 is independently methyl or hydrogen, g is 0 to 2, and m and n are 0.
The composition of the filament of the present invention also comprises a high viscosity silicone, having a kinematic viscosity from 60,000 to 100 million cSt.
Silicones, also known as polyorganosiloxanes or polysiloxanes, are polymers having alternate silicon and oxygen atoms in the skeletal structure, and containing silicon-bonded hydrocarbon radicals, the hydrocarbon radicals being attached to the silicon through carbon-silicon linkages wherein the silicone have the general formula RrSiO(4-r/2), wherein r is 0, 1, 2 or 3, with the proviso that the average numerical value of r is in the range from 1.9 to 2.1, and wherein each R is independently hydrogen, hydroxyl, or substituted or unsubstituted hydrocarbon radicals such as, for instance, alkyl radicals (e.g., methyl, ethyl, and propyl); aryl radicals (e.g., phenyl, naphthyl); alkaryl radicals (e.g., tolyl, xylyl); aralkyl radicals (e.g., benzyl, phenyl-ethyl); alkoxy, cycloalkyl radicals such as cyclohexyl; and heterocyclic radicals. The hydrocarbon radical may be substituted with essentially inert substituents as, for example, halogens. The silicone resins are 3-dimensional cross-linked relatively rigid solid polymers when hardened or cured. High viscosity silicone, as used herein, represents a wide range of polysiloxane materials having a high molecular weight and include, for example, fluids and gums with a viscosity ranging from about 500,000 to 100 million cSt, preferably from about 600,000 to 20 million, more preferably from about 600,000 to 12 million cSt. All ranges mentioned herein include all subranges, e.g. 550,000; 925,000; 3.5 million.
Suitable silicones include, but are not limited to vinyl-terminated PDMS with a viscosity of 60,000 cSt and with a viscosity of 165,000 cSt, each respectively available as DMS-V46 and as DMS-V52 from Gelest, Inc.; high viscosity linear polydimethylsiloxane fluids ranging in viscosity from 300,000 cSt to 20,000,000 cSt available from CLEARCO Products Co., Inc.; ultrahigh-molecular-weight polydimethylsiloxane with a viscosity from 10-20 million cSt available from Wacker Chemie AG as GENIOPLAST® Gum; GENIOPLAST® Pellet P an ultrahigh-molecular-weight polydimethylsiloxane in pellet form comprised of a combination of 100 parts methyl vinyl functional polydiorganosiloxane with up to 200 parts fumed silica and up to 20 parts of boric acid, as described in U.S. Pat. No. 7,897,666 by Daniel Berg; and GENIOPLAST® Pellet S an ultrahigh-molecular-weight polydimethylsiloxane in pellet form comprising Trimethylsiloxy-endcapped poly(dimethylsiloxane-co-vinylmethylsiloxane) (70 weight percent) on fumed silica (30 weight percent) and treated with boric acid to form a boro-silicone as described in U.S. Pat. No. 7,250,127 by Michael Geck et al.
These high viscosity silicones, often characterized as silicone gums which are comprised of about 20-100% siloxane polymers. The term “gum” means a silicone polymer having a degree of polymerization sufficient to provide a silicone having a gum-like texture. Also, the silicone gum may also be purchased in the form of a solution or dispersion in a silicone compatible vehicle such as volatile or nonvolatile silicone.
Illustrative gums will comprise poly(dimethylsiloxanes), copolymers of dimethylsiloxane and methylvinylsiloxane, copolymers of dimethylsiloxane and diphenylsiloxane, terpolymers of dimethylsiloxane, phenylmethylsiloxane, and methylvinylsiloxane, terpolymers of dimethylsiloxane, methylvinylsiloxane and methyltrifluoropropylsiloxane, copolymers of dimethylsiloxane and ethylvinylsiloxane, and copolymers of dimethylsiloxane and methylcyanoethylsiloxane. The homo- and copolymers can be blocked at the ends, e.g., with triorganosiloxy units, such as trimethylsiloxane, dimethylvinylsiloxane, dimethylphenylsiloxane units, and the like. Preferably, the organo substituents in the gum will be selected from methyl, vinyl, phenyl or trifluoropropyl. However, other organic radicals may also be included, such as ethyl, propyl, octadecyl, allyl, cyclohexenyl, naphthyl, chloromethyl, bromophenyl, and the like.
The compositions can be vulcanized or rendered vulcanizable by any methods conventional in silicone rubber technology, e.g., by heat or high energy radiation. Preferably, however, the composition will include a small but effective amount of a heat-reactive vulcanization catalyst. The preferred such catalysts will be organic peroxides and organic per-esters, for example, benzoyl peroxide, tertiary butyl peracetate, dicumyl peroxide, cumyl tert. butyl peroxide, 2,5-di-tert. butyl peroxy-2,5-dimethyl hexane, 2,4-dichlorobenzoyl peroxide, tert. butyl perbenzoate, hexylene glycol perbenzoate, and the like. The preferred catalysts are 2,4-dichlorobenzoyl peroxide and benzoyl peroxide.
One method to produce pelletized organopolysiloxane material is to take 100 parts of one or more dipolyorganosiloxane(s) end-capped by trialkylsiloxy groups, most preferably by trimethylsiloxy groups, and composed of from 70 to 100%, more preferably from 90 to 100%, of dimethylsiloxane units, and from 0 to 30%, more preferably from 0 to 10%, of alkenylmethylsiloxane units, most preferably vinylmethylsiloxane units, with a viscosity which is preferably from 103 to 108 cSt at 25° C., more preferably from 105 to 108 cSt at 25° C., are mixed in a kneader operated at from 100 to 250° C., most preferably at from 120 to 200° C., preferably with from 0 to 50 parts, more preferably from 0.1 to 30 parts, of additives (D), and preferably with from 1 to 200 parts, more preferably with from 30 to 100 parts, of one or more reinforcing or non-reinforcing fillers (B), or a mixture of the two, and preferably kneaded for from 10 minutes to 12 hours, more preferably from 30 minutes to 6 hours.
The poly(diorganosiloxane)gums are highly viscous masses or gummy elastic solids depending on the state of condensation, the condensing agent employed, and the starting organopolysiloxane used to make the gummy material. A typical gum is obtained by the condensation of a liquid poly(organosiloxane) with one of the well-known condensing agents, e.g., ferric chloride hexahydrate, phenyl phosphoryl chloride, alkaline condensing agents, such as potassium hydroxide, sodium hydroxide and the like. A typically useful gum is prepared by mixing together about 95 mole % of octamethylcyclotetrasiloxane, and about 5 mole % decamethyltetrasiloxane at a temperature of 150°-175° C. for about 4 hours with about 0.01% potassium hydroxide until a highly viscous gum is obtained
Furthermore, the polyorganosiloxanes may include reinforcing and/or non-reinforcing fillers. Examples of reinforcing fillers are fumed or precipitated silicas. If reinforcing fillers are used, it is preferable to use fumed or precipitated silicas with BET surface areas of at least 50 m2/g, more preferably at least 100 m2/g. Preferably, the silicone comprises 60 to 80 weight percent of silicone gum and 20 to 40 weight percent of fumed silica.
Examples of non-reinforcing fillers are quartz flour, diatomaceous earth, calcium silicate, zirconium silicate, zeolites, metal oxide powder such as aluminum, titanium, iron, or zinc oxide, barium silicate, barium sulfate, gypsum, polytetrafluoroethylene. Furthermore, can be used as fillers fibrous components such as glass and plastic fibers.
Generally, where the composition includes a filler, the filler may be a single filler or a mixture of fillers. The preferred fillers are finely divided reinforcing fillers, e.g., silica, either aerogel or fumed, having a specific surface area of 50 to 350 m2/g. Other fillers, such as semi-reinforcing and extending fillers, such as diatomaceous earth, ground quartz, alkaline earth sulfates or silicates (e.g., zirconium silicate), metallic oxides, such as iron oxide, zinc oxide, aluminum oxide, titanium dioxide, and the like, and carbon black, can also be present.
The filament can, optionally, further comprise one or more additives known in the thermoplastics art. Such additives can include, for example, stabilizers, antioxidants, dyes, pigments, anti-static agents, mineral oil, metal deactivators, and combinations thereof. When present, the one or more additives can be used in a total amount of up to 2 weight percent, based on the weight of the filament. Within this range, the additive amount can be up to 1 weight percent, or 0.2 to 1 weight percent.
In a second embodiment, an article of the present invention comprises a structure comprising a model and a support structure wherein at least a portion of a surface of the support structure is adhered to at least a portion of a surface of the model, wherein the model comprises a build material and wherein the support structure comprises an amorphous, thermoplastic resin and a high viscosity silicone.
Yet a third embodiment of the present inventiont is a method of fused filament fabrication to print a model structure from a build material and a support structure for the model from an amorphous, thermoplastic resin.
Each of the aforementioned support filaments, and their compositions are suitable for the article and method provided that the amorphous thermoplastic resin in the support filament does not contain the same base polymer as that included within the build material. In one embodiment the support filament's Tg is within 30° C. of the Tg or melting point of the build material.
Build materials suitable for the model include, but are not limited to, polyetherimides, as defined above, copolymers of Bisphenol A carbonate, polyarylether ketones, polyester carbonates, polysulfones, polyphenylene sulfides, polyamides, polyphthalamides and polyimides.
In the method of fused filament fabrication, the method comprises melting a portion of a first filament to form a first thermally-solidifiable material in molten form, and dispensing the first thermally-solidifiable material in molten form in a predetermined pattern so as to define a three-dimensional object; and melting a portion of a second filament to form a second thermally-solidifiable material in molten form, and, in coordination with the dispensing the first thermally solidifiable material, dispensing the second thermally-solidifiable material in molten form so as to define a support structure for the three-dimensional object; wherein the second thermally-solidifiable material comprises (a) 95.5 to 99.5 weight percent of an amorphous, high heat thermoplastic resin, having a Tg from 165° C. to 350° C., and (b) 0.5 to 4.5 weight percent of a high viscosity silicone, having a kinematic viscosity from 60,000 to 100 million cSt, based upon the combined weight of the thermoplastic resin and silicone in the filament, and wherein the silicone is immiscible with the thermoplastic resin.
As used herein, a “thermally-solidifiable material” is a material capable of being solidified on cooling from a molten state.
In one embodiment, the first thermally-solidifiable material has a glass transition temperature or a melting point in a range of within 30° C. of the Tg of the second thermally-solidifiable material.
The method further comprises the step of removing at least a portion of the support structure from the three dimensional model comprising physically separating at least a portion of the support structure from the three-dimensional model.
All of the variations in support material described above in the context of the support filament apply as well to the method of additive manufacturing. The invention includes at least the following embodiments.
Embodiment 1: An article of manufacture comprising a filament for use in 3D printing wherein the filament comprises: (a) 95.5 to 99.5 weight percent of an amorphous, thermoplastic resin having a glass transition temperature, as measured by differential scanning calorimetry, from 165° C. to 350° C., and (b) 0.5 to 4.5 weight percent of a high viscosity silicone having a kinematic viscosity from 60,000 to 100 million centistokes at 25° C.; based upon the combined weight of the thermoplastic resin and silicone in the filament, wherein the silicone is immiscible with the thermoplastic resin.
Embodiment 2: An article of embodiment 1 wherein the silicone comprises a silicone gum.
Embodiment 3: An article of embodiments 1 and 2 wherein the silicone further comprises a silica.
Embodiment 4: An article of embodiment 1 wherein the silicone comprises: (a) 60 to 80 weight percent of silicone gum and (b) 20 to 40 weight percent of fumed silica.
Embodiment 5: An article of embodiments 1 to 4 wherein the silicone gum comprises a boro-silicone.
Embodiment 6: An article of embodiments 1 to 5 wherein the filament has a diameter of 1 to 5 millimeters with a standard deviation of 0.005 to 0.1 millimeters.
Embodiment 7: An article of manufacture comprising: (a) a support structure comprising: (i) 95.5 to 99.5 weight percent of an amorphous, high heat thermoplastic resin, (ii) 0.5 to 4.5 parts by weight percent of a high molecular weight silicone, based upon the combined weight of the thermoplastic resin and silicone in the support structure, and (b) a three dimensional model comprising a second thermoplastic resin wherein the second thermoplastic resin and the high heat resin are not the same, and wherein at least a portion of a surface of the support structure is adhered to at least a portion of a surface of the three dimensional model.
Embodiment 8: An article of claim 7 wherein the silicone comprises a silicone gum.
Embodiment 9: An article of embodiments 7 and 8 wherein the silicone further comprises a silica.
Embodiment 10: An article of embodiment 8 wherein the silicone comprises: (a) 60 to 80 weight percent of silicone gum and (b) 20 to 40 weight percent of fumed silica.
Embodiment 11: An article of embodiments 7 to 10 wherein the silicone gum comprises a boro-silicone.
Embodiment 12: An article of embodiments 7 to 11 wherein the second thermoplastic resin comprises polyetherimides, copolymers of Bisphenol A carbonate, polyarylether ketones, polyester carbonates, polysulfones, polyphenylene sulfides, polyamides, polyphthalimides and polyimides.
Embodiment 13: A method of fused filament fabrication, the method comprising: melting a portion of a first filament to form a first thermally-solidifiable material in molten form, and dispensing the first thermally-solidifiable material in molten form in a predetermined pattern so as to define a three-dimensional model; and melting a portion of a second filament to form a second thermally-solidifiable material in molten form, and, in coordination with the dispensing the first thermally solidifiable material, dispensing the second thermally-solidifiable material in molten form so as to define a support structure for the three-dimensional model; wherein the second thermally-solidifiable material comprises, (a) 95.5 to 99.5 weight percent of an amorphous, high heat thermoplastic resin, and (b) 0.5 to 4.5 weight percent a high viscosity silicone, based upon the combined weight of the thermoplastic resin and silicone in the filament, wherein the silicone is immiscible with the thermoplastic resin.
Embodiment 14: The method of embodiment 13 wherein the silicone comprises: (a) 60 to 80 weight percent of silicone gum and (b) 20 to 40 weight percent of fumed silica, and wherein the first thermally-solidifiable material has a glass transition temperature or a melting point in a range of within 30° C. of the Tg of the second thermally-solidifiable material.
Embodiment 15: The method of embodiments 13 to 14, further comprising physically separating at least a portion of the support structure from the three-dimensional model.
All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. Each range disclosed herein constitutes a disclosure of any point or sub-range lying within the disclosed range.
The invention is further illustrated by the following non-limiting examples.
Components used to form comparative and exemplary filaments are summarized in Table 1.
Compositions used to prepare comparative and exemplary filaments are summarized in Table 2, where component amounts are expressed in units of weight percent based on the total weight of the composition. Resin pellets were loaded into a desiccant dryer (Dri-Air; East Windsor, Conn., USA) a day before filament extrusion. Filament was extruded by separately feeding each composition through an extruder (FET, Leeds, UK) equipped with a precision melt pump. The screw for this extruder had a length to diameter ratio of 30:1, with lengths of 10D in the convey zone, 12D in the transition zone, and 8D in the metering section. The melt temperatures were set at about 280° C. to 300° C. The extrudate exited vertically out of a four mm die orifice inner diameter and 16 mm die length and was stretched to form monofilament while being air cooled. The puller line speed was adjusted to achieve a final filament diameter of 1.8 millimeters. On-line diameter measurements were acquired using a dual-axis high speed and high precision scanning micrometer (Keyence; Itasca, Ill., USA).
The glass transition Temperature (Tg) of each filament was determined using differential scanning calorimetry, in accordance with ASTM D3418, with a 20° C./min heating rate (hereinafter “DSC”) by using a TA Instruments Q1000 Differential Scanning calorimeter. in a temperature range from 0 to 250° C. at a heating rate of 20° C. per minute under nitrogen flow.
After extruding a filament for each composition in Table 2, the quality of each of these filaments was evaluated. A filament extrusion rating of “−” indicates the, using the aforementioned procedure, the composition was not extruded to a targeted diameter within +/−0.010 millimeter or could not achieve a standard deviation of within 0.010 millimeter. A rating of “+” indicates the composition was extruded to a targeted diameter within +/−0.010 millimeter and with a standard deviation of within 0.010 millimeter.
Experimental structures, including model structures in various simple and complex geometries and breakaway support structures, were printed using Stratasys 400mc and 900mc printers using a polyetherimide filament, made from ULTEM™ 9085 resin, as the model material and using each filament of Table 2 as the support material. As an experimental control, the same structure designs were printed using polyetherimide, model or build filament, made from ULTEM™ 9085 resin and a polysulfone support filament, specifically a filament comprising a phenol, 4,4′(1-methylethylidene)bis-polymer with 1,1′-sulfonylbis(4-chlorobenzene), (3-chloropropyl)trimethoxysilane-terminated resin, available from Stratasys Ltd. and disclosed as a breakaway support for models made from ULTEM™ 9085 resin. Both the experimental structures and support structures were concurrently printed together using the printer's support temperature profile for filament made from ULTEM™ 9085 resin. Under this temperature profile, a T16 or T20 tip was used to print the model, and a T16 tip was used to print basic support structures.
During printing, the degree of oozing and the quality of printing of each support material from the T16 tip was evaluated. Oozing of the support material can create unplanned support material strands or hairs that may degrade the print quality of the model negatively and lead to support material being embedded within the model being printed. A rating of “Yes” indicates that an unacceptable level of oozing was observed that would likely degrade the quality of the printed model. A rating of “No” indicates slight oozing was observed that did not adversely affect the print quality of the model.
The quality of the printing of support structures using each support material was evaluated based upon the printing factors: tool path tracking, self- and cross-adhesion, overhang catch (at 15, 30, 45, and 50 degrees), surface quality, ability to support printing the design, and consistent printing with no printer jams. A printing quality rating of “Good” indicates good self-adhesion, good overhang catch at 15, 30, 45, and 50 degrees, good surface quality, and good ability to support several designs. A printing quality rating of “Poor” indicates one or more of the following: poor overhang catch, poor surface quality, tip clogging, inability to support several designs, missing toolpaths, overfilling or under filling. A printing quality rating of “Medium” indicates some degree of under filling and gaps in toolpaths. A rating of N.D. means that the print quality was not determined.
After completing printing the model and support structure, for each different support filament, the ability, to readily break away each support material from the ULTEM 9085 resin model, at room temperature, was qualitatively evaluated (pliability, ease of breaking into, effort needed to remove, and size of pieces breaking off). An ease of removal rating of “Good” indicates good pliability, ease of breaking into support structure, ease of removal of all support structure, and comes off in large pieces. It also indicates that the support material comes off easily compared to commercial polysulfone support material for ULTEM™ 9085 resin build material. A rating of “Poor” means one or more of the following: poor pliability, difficulty breaking into the support structure, inability to remove all support structure, and support structure removal in small pieces.
As shown in Table 2, the support filament compositions that performed significantly better in terms of ease of making filaments, mitigation of support material oozing, overall print quality and subsequent ease of removal from the printed model, particularly when compared to the polysulfone commercial support filament, used herein as a control, or a support filament consisting of APEC® 2097 resin (C3 in Table 2). The control support filament was found to provide good performance in terms of filament extrusion, lack of oozing and print quality. However, it was also found that control filament support structures were very difficult to remove from the models made from ULTEM™ 9085 resin. The APEC® 2097 resin (C3) support filament was found to provide good performance in terms of filament extrusion and print quality. However, it exhibited unacceptable levels of oozing and was also difficult to remove from the models made from ULTEM™ 9085 resin. The support filaments exemplified herein, particularly Ex5, Ex6, Ex7, Ex8, Ex9 and Ex10, still demonstrated good performance in terms of filament extrusion and print quality but, in an unexpected improvement as compared to the control and the APEC® 2097 resin filaments' performance, also showed acceptable levels of oozing and good ease of removal from the models made from ULTEM™ 9085 resin.
| Number | Date | Country | Kind |
|---|---|---|---|
| 19154789.2 | Jan 2019 | EP | regional |
This application claims priority to European Application No. 19154789.2, filed Jan. 31, 2019, which claims priority to U.S. Provisional Application No. 62/781,218 filed Dec. 18, 2018, which are incorporated by reference herein in their entirety.
| Number | Date | Country | |
|---|---|---|---|
| 62781218 | Dec 2018 | US |
