US20230021553A1 - Spatially controlled functionality of polymeric products - Google Patents

Spatially controlled functionality of polymeric products Download PDF

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Publication number
US20230021553A1
US20230021553A1 US17/635,768 US202017635768A US2023021553A1 US 20230021553 A1 US20230021553 A1 US 20230021553A1 US 202017635768 A US202017635768 A US 202017635768A US 2023021553 A1 US2023021553 A1 US 2023021553A1
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Prior art keywords
polymer
component
polymerizable component
product
functional
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US17/635,768
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Kathleen SAMPSON
Bhavana Deore
Chantal Paquet
Thomas Lacelle
Patrick Roland Lucien Malenfant
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National Research Council of Canada
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National Research Council of Canada
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Priority claimed from PCT/IB2019/058923 external-priority patent/WO2020079669A1/en
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Priority to US17/635,768 priority Critical patent/US20230021553A1/en
Assigned to NATIONAL RESEARCH COUNCIL OF CANADA reassignment NATIONAL RESEARCH COUNCIL OF CANADA ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: PAQUET, Chantal, DEORE, BHAVANA, LACELLE, Thomas, MALENFANT, PATRICK ROLAND LUCIEN, SAMPSON, Kathleen
Publication of US20230021553A1 publication Critical patent/US20230021553A1/en
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00009—Production of simple or compound lenses
    • B29D11/00355—Production of simple or compound lenses with a refractive index gradient
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F22/10—Esters
    • C08F22/12—Esters of phenols or saturated alcohols
    • C08F22/18—Esters containing halogen
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00—Simple or compound lenses
    • G02B3/0087—Simple or compound lenses with index gradient
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01Q—ANTENNAS, i.e. RADIO AERIALS
    • H01Q15/00—Devices for reflection, refraction, diffraction or polarisation of waves radiated from an antenna, e.g. quasi-optical devices
    • H01Q15/02—Refracting or diffracting devices, e.g. lens, prism
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01Q—ANTENNAS, i.e. RADIO AERIALS
    • H01Q9/00—Electrically-short antennas having dimensions not more than twice the operating wavelength and consisting of conductive active radiating elements
    • H01Q9/04—Resonant antennas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
    • B29K2033/04—Polymers of esters
    • B29K2033/08—Polymers of acrylic acid esters, e.g. PMA, i.e. polymethylacrylate
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/008—Surface plasmon devices

Definitions

  • the disclosure relates to functional and/or functional precursor products, formulations for making the products, methods of making the products, and uses thereof.
  • Functional products are products that perform at least one function. In the traditional sense, it would encompass a product that has, for example, one or more chemical, mechanical, magnetic, thermal, electrical, optical, electrochemical, protective, and catalytic properties. It could also, or instead, include a product that has an aesthetically pleasing property.
  • 3D printing is an emerging technology poised to transform manufacturing of functional products.
  • Stereolithographic (SLA) printing is one of a number of 3D printing techniques that faces this problem.
  • the bulk of the feedstock materials are based on polymer resins and as a result the technique is limited to generating products with basic function (e.g. structural).
  • New formulations that incorporate functionality would allow a 3D printing technique to generate structural components with specific functions (e.g. electrical conduction).
  • 3D printed elastomeric structures were formed by digital light processing (DLP), once printed and processed, the structure is subsequently immersed in a solution of silver nanoparticles and exposed to hydrogen chloride vapors.
  • DLP digital light processing
  • Magdassi, S. et al., Highly Stretchable and UV Curable Elastomers for Digital Light Processing Based 3 D Printing Adv. Mater. 2017, 29, 1606000.
  • a polymer based ink was developed that prints a porous structure.
  • the porous structure was put under vacuum and dipped in a dispersion of silver nanoparticles.
  • the structure was then sintered. (Magdassi, S. et al., 3 D Printing of Porous Structures by UV - curable O/W Emulsion for Fabrication of Conductive Objects , J. Mater Chem. C. 2015, 3, 2040).
  • 3D printing feedstock materials e.g. resin or filament
  • the materials require multiple and lengthy steps post-printing to generate, for example, a functional 3D structure and, for example, especially selective positioning of functionality in a 3D structure.
  • a method for making a product comprising: a) combining at least one first polymerizable component and at least one second polymerizable component to form a composition; and b) polymerizing the at least one first polymerizable component to form at least one first polymer structure, wherein at least two phases are formed from the at least one first polymer structure and the at least one second polymerizable component, and wherein the product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product.
  • a product comprising: i) at least one first polymer structure comprising at least one first polymer; and ii) at least one second polymerizable component, wherein the product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product.
  • a formulation for making a product comprising a composition having at least one first polymerizable component and at least one second polymerizable component, the at least one first polymerizable component is polymerizable to form at least one first polymer structure, wherein at least two phases are formed from the at least one first polymer structure and the at least one second polymerizable component, and the product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product.
  • a method for making a product comprising a) polymerizing at least one first polymerizable component to form at least one first polymer structure; b) combining the at least one first polymer structure and at least one first component, wherein the at least one first component comprises at least one functional component, at least one functional precursor component, or combinations thereof, and wherein the product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product.
  • a product comprising: i) at least one first polymer structure comprising at least one first polymer; and ii) at least one first component, wherein the product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product.
  • a method for making a product comprising: a) combining at least one first polymerizable component and at least one polymer and/or polymer derivative to form a composition; and b) polymerizing the at least one first polymerizable component to form at least one first polymer structure, wherein at least two phases are formed from the at least one first polymer structure and the at least one polymer and/or polymer derivative, and wherein the product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product.
  • a product comprising: i) at least one first polymer structure comprising at least one first polymer; and ii) at least one at least one polymer and/or polymer derivative, wherein the product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product.
  • a formulation for making a product comprising a composition having at least one first polymerizable component and at least one at least one polymer and/or polymer derivative, the at least one first polymerizable component is polymerizable to form at least one first polymer structure, wherein at least two phases are formed from the at least one first polymer structure and the at least one at least one polymer and/or polymer derivative, and the product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product.
  • FIG. 1 shows a schematic of some embodiments of a method.
  • FIGS. 2 A, 2 B, and 2 C show examples of 3D printed products. The formulations used to make these products are described in Examples 1-15.
  • FIGS. 3 A- 3 D shows scanning electron microscope (SEM) images of examples of 3D printed cylinders ( FIGS. 3 A- 3 C ) and a perspective view ( FIG. 3 D ) of where the SEM images were taken on the cylinders (see circle).
  • SEM scanning electron microscope
  • FIGS. 4 A and 4 B show cross-sectional SEM images of the interface of an example of a 3D printed product.
  • FIG. 5 shows thermal gravimetric analysis (TGA) of silver SLA 3D product cured in air. The formulation used to make this product is described in Example 5.
  • FIGS. 6 A and 6 B show optical images of a 5 ⁇ L drop of water on a 3D printed tile containing a) 0 wt. %, and b) 20 wt. % respectively of 1H,1H-perfluorooctyl methacrylate.
  • the formulation used to make this product is described in Example 15.
  • FIG. 7 shows a graph of contact angles of 3D printed tiles and of UV-cured films vs. % wt. fluorinated methacrylate monomer.
  • the formulation used to make this product is described in Example 15.
  • FIG. 8 shows the surface concentration of silver of 3D printed products made from resins with varying amounts of cross-linking agents. The formulations used to make these products are described in Examples 16-26 and 31-41.
  • FIG. 9 shows the resistance of the silver coating on 3D printed products made from resins with varying amounts of cross-linking agents.
  • the formulations used to make these products are described in Examples 16-26 and 31-41.
  • FIG. 10 shows the concentration of silver within a 3D printed cylinder.
  • a silver coating can form where the concentration of silver decreases with increased distance from the surface of the cylinder.
  • the silver concentrations are substantially uniform across the cross-section of the product.
  • FIG. 11 shows SEM images and schematic of a strain sensor made from a 3D printed product.
  • the 3D silver product was prepared using the resin composition described in Example 54. As the strain sensor is compressed, the silver nanoparticles made contact and increased the conductivity of the silver film.
  • FIG. 12 shows the results of a cycling experiment where the electrical resistance of a 3D printed strain sensor was compressed by various length scales. As the sample is compressed, the resistance drops.
  • the 3D silver product was prepared using the formulation described in Example 54.
  • FIG. 13 shows representative photographs of the bacterial inhibition zones created by the different scaffolds against E. coli.
  • E. coli was plated on LB agar at ⁇ 1 ⁇ 109 cfu/ml, 18 hr growth.
  • the 3D products were prepared using the formulation described in Example 57.
  • FIG. 14 shows representative photographs of antibacterial performance of different scaffolds against TG1 ( E. coli ). 24 hr growth of TG1 with 3D silver products and control product. The 3D silver products were prepared using the formulation described in Example 57.
  • FIG. 15 shows a growth curve of E. coli TG1 with 3D silver products and control product.
  • the 3D silver products were prepared using the formulation described in Example 57.
  • FIG. 16 shows a growth curve of E. coli TG1 with broth of silver product supernatant (42 hr).
  • the 3D silver products were prepared using the formulation described in Example 57.
  • FIG. 17 shows SEM images of 3D TiO 2 products printed without toluene (a, b and c) and with toluene (d, e and f).
  • the 3D TiO 2 products were prepared using the formulations described in Examples 50 and 51.
  • FIG. 18 shows wt % of TiO 2 as a function of distance from the surface of the 3D TiO 2 products.
  • the 3D TiO 2 products were prepared using the formulations described in Examples 50 and 51.
  • FIG. 19 shows SEM images of 3D Barium Strontium Titanate (BST) product.
  • the 3D BST product was prepared using the formulation described in Example 52.
  • FIG. 20 shows a) SEM images of the cross-section of a printed cylinder with iron oxide nanoparticles.
  • the nanoparticles appear as bright areas in the SEM; energy dispersion spectroscopy (EDS) analysis of the SEM mapping out b) carbon and c) iron in the sample.
  • EDS energy dispersion spectroscopy
  • the 3D iron product was prepared using the formulation described in Example 53.
  • FIG. 21 shows the contact angle of 3D printed tiles printed using photoresins with three different fluorinated monomers.
  • the 3D printed tiles were prepared using the formulation described in Example 58.
  • FIG. 22 shows the contact angle of 3D printed tiles, printed using 20% wt. 2,2,3,4,4,4-hexafluorobutyl methacrylate, as a function of depth of the tile.
  • the 3D printed tiles were prepared using the formulation described in Example 58.
  • FIG. 23 shows an example of vat polymerization 3D printing.
  • FIG. 24 shows an example of photopolymerization induced phase separation (PIPS) for controlled placement of functionality in a 3D printed product.
  • PIPS photopolymerization induced phase separation
  • FIG. 25 shows another example of photopolymerization induced phase separation (PIPS) for controlled placement of functionality in another 3D printed product.
  • PIPS photopolymerization induced phase separation
  • FIG. 26 shows (a) Computer aided design (CAD) image of hexagonal patterned sheets with “spaces” in between the individual hexagons and sheets of hexagons. (b) and (c) Scanning electron microscope (SEM) with a backscatter electron detector (BSE) images of commercial Form Labs Ceramic resin 3D printed in hexagonal design structure. The image on the bottom left (b) shows the hexagonal pattern (area denoted by reference numeral 1) with a border (areas denoted by reference numerals 2 and 3) and spaces in between (area denoted by reference numeral 4).
  • CAD Computer aided design
  • SEM Scanning electron microscope
  • BSE backscatter electron detector
  • the particle density (the four images on the right in (c)) changes based on the location in and around the hexagons with less particles at reference numeral 3 along the hexagonal border compared to the actual hexagonal shape and spaces in between (reference numerals 1, 2, and 4).
  • the 3D printed hexagonal platelets/sheets were prepared using the formulation described in Example 60a.
  • FIG. 27 shows (a) Computer-aided design (CAD) image of hexagonal 3D printed platelets/sheets with “spaces” in between and support bridges to hold the individual platelets/sheets together. (b) and (c) Microscope images of 3D printed structure with one photopolymer (ethylene glycol phenyl ether acrylate:1,6 hexanediol diacrylate) and one functional material (hydride terminated polydimethylsiloxane). The hexagonal platelets and spaces both contain cured polymer, but the spaces are more transparent while the platelets are opaque due to the phase separated polydimethylsiloxane functional material.
  • the 3D printed hexagonal platelets/sheets were prepared using the formulation described in Example 60b.
  • FIG. 28 shows (a) Scanning electron microscope (SEM) images of the cross-section of ethylene glycol phenyl ether acrylate:1,6-hexanediol diacrylate photopolymer with phase separated hydride terminated polydimethylsiloxane.
  • SEM Scanning electron microscope
  • EDS Energy dispersive X-ray spectroscopy
  • FIG. 29 shows scanning electron microscope (SEM) images of the cross-section of ethylene glycol phenyl ether acrylate:1,6-hexanediol diacrylate photopolymer with phase separated hydride terminated polydimethylsiloxane.
  • SEM scanning electron microscope
  • FIG. 30 shows a-d) top and e-f) side images of the custom designed structure of example platelets separated by spaces and held together with support bridges using a stereolithographic printer.
  • a, c, and e) show the structure after printing and before infiltration with the thermal curable resin.
  • b, d, f) show the structure after infiltration and thermal curing of the second resin.
  • the 3D printed structure and infiltration methods are described in Example 59a.
  • FIG. 31 shows a) Image of an example structure with bottom of the structure transparent and top dyed darker with the color of the second photoinitiator and co-initiator. b) Raman spectroscopy mapping at the interface between the top and bottom of the structure in a) with respect to the change in —C—H peak intensity relative to the baseline at ⁇ 2920 cm ⁇ 1 . The method is described in Example 62a.
  • any aspects described as “comprising” certain components may also “consist of” or “consist essentially of,” wherein “consisting of” has a closed-ended or restrictive meaning and “consisting essentially of” means including the components specified but excluding other components except for materials present as impurities, unavoidable materials present as a result of processes used to provide the components, and components added for a purpose other than achieving the technical effect of the invention.
  • a composition defined using the phrase “consisting essentially of” encompasses any known acceptable additive, excipient, diluent, carrier, and the like.
  • a composition consisting essentially of a set of components will comprise less than 5% by weight, typically less than 3% by weight, more typically less than 1%, and even more typically less than 0.1% by weight of non-specified component(s).
  • phrases “at least one of” is understood to be one or more.
  • the phrase “at least one of . . . and . . . ” is understood to mean at least one of the elements listed or a combination thereof, if not explicitly listed.
  • “at least one of A, B, and C” is understood to mean A alone or B alone or C alone or a combination of A and B or a combination of A and C or a combination of B and C or a combination of A, B, and C.
  • At least one of at least one of A, at least one of B, and at least one of C is understood to mean at least one of A alone or at least one of B alone or at least one of C alone or a combination of at least one of A and at least one of B or a combination of at least one of A and at least one of C or a combination of at least one of B and at least one of C or a combination of at least one of A, at least one of B, and at least one of C.
  • composition is understood to mean having two or more components/elements.
  • a substantially homogeneous mixture is understood to mean a substantially uniform mixture or combination of components.
  • morphology is understood to mean a shape and size of an area or a volume (e.g. the texture or topography of a surface; the habit of a crystal; the distribution of phases in a material).
  • phase is interchangeably used herein with “morphology”, “layer”, “zone”, and/or “structure”. These terms are understood to mean a region of a functional product and/or a functional precursor product having an area or volume of material with relatively uniform chemical and/or physical properties. For example, one phase or region may have uniform chemical and/or physical properties and another phase or region may have different uniform chemical and/or physical properties. It is understood that a given phase or region having relatively uniform chemical and/or physical properties can, but does not necessarily require, homogeneity throughout the phase. An interface between phases may also constitute a distinct phase. For example, a phase may have a component present in amounts falling within a desired concentration range.
  • phases may arise from printing using distinct formulations, in sequence, to produce distinct regions, or may arise out of polymerization processes designed to result in product component phase separation, or a concentration gradient.
  • phases may be characterized according to one or more chemical and/or physical properties having regard to one or more components in order to delineate between phases/regions of a functional product and/or a functional precursor product.
  • a combination of one or more phases/regions may be considered a single concentration gradient.
  • resin is understood to be a solid or viscous material which provides a polymer after polymerization via, for example, curing.
  • concentration gradient is understood to be spatial positioning of one or more molecules/ions from a region having a higher concentration of the one or more molecules/ions to a region having a lower concentration of the one or more molecules/ions.
  • orthogonal polymerization is understood to include the ability to perform multiple polymerization reactions independently (orthogonally), for example, in a single reaction vessel.
  • a mechanism of a polymerization reaction of at least one first polymerizable component is different than a mechanism of the polymerization reaction of at least one second polymerizable component.
  • a sequence of chemical reaction(s) of converting at least one first polymerizable component that has at least one first monomer and/or at least one first cross-linking agent to at least one first polymer differs from a sequence of chemical reaction(s) of converting at least one second polymerizable component that has at least one second monomer and/or at least one second cross-linking agent to at least one second polymer.
  • the chemical reaction(s) include, for example, radical polymerization (e.g. involves the transfer of a radical from an initiator or building block to another monomer/crosslinking agent), cationic polymerization (e.g. involves the transfer of charge from a cationic initiator or building block to another monomer/crosslinking agent), and thermal polymerization (e.g. involves the addition of two or more molecules to form a larger molecule and eventually a polymer).
  • radical polymerization e.g. involves the transfer of a radical from an initiator or building block to another monomer/crosslinking agent
  • cationic polymerization e.g. involves the transfer of charge from a cationic initiator or building block to another monomer/crosslinking agent
  • thermal polymerization e.g. involves the addition of two or more molecules to form a larger molecule and eventually a polymer.
  • thermodynamic miscibility is understood to be governed by the Gibbs free energy of mixing.
  • the molecular weight increases causing the entropy of mixing to be reduced which decreases the miscibility of a second monomer and/or a second cross-linking agent in the polymer/monomer mixture.
  • the degree of phase separation can depend on the solubility and balance of intermolecular forces between each component (each set of monomer(s)/crosslinker(s)).
  • Incompatible functional groups such as polar vs. non-polar, steric vs. non-steric, aliphatic vs. aromatic, aliphatic vs. inorganic, can, for example, influence the solubility and degree of phase separation.
  • modulus of elasticity of a polymer is understood to be a number that measures an object or substance's resistance to being deformed elastically (i.e., non-permanently) when a force is applied to it.
  • tensile strength of a polymer is understood to be a measure of the ability of a polymer to withstand a longitudinal stress before permanent deformation occurs.
  • the term “functional product” is considered herein to be a product that performs at least one function. It may encompass a product that has, for example, one or more chemical, mechanical (including structural), magnetic, thermal, electrical, optical, electrochemical, protective, and catalytic properties. It could also, or instead, include a product that has an aesthetically pleasing property.
  • Functional products can include a functional material such as a functionally graded material (FGM), and more specifically, a functionally graded composite material (FGCM).
  • FGMs may be applied in a variety of industries, including, for example, aerospace, automobile, biomedical, defence, electrical/electronic, energy, marine, mining, opto-electronics, thermoelectronics, dentistry, and sports. FGMs may be used under a variety of conditions, including extreme temperature and wear conditions.
  • interface refers to a region or surface of a functional and/or functional precursor product, which can include a surface of an intermediate structure in or comes into contact with another region/phase/material.
  • the interface may be a functional and/or functional precursor coating on the product (eg at an exterior surface) or as a layer/region within the product.
  • the product may be an intermediate structure, which is further processed (e.g. further layered/coated) such that the exterior surface now acts as an interface between the intermediate structure and the additional layer/coating.
  • the interface may be a graded functional and/or functional precursor material, the interface may be the region of the product where there is a certain concentration range of functional and/or functional precursor components to provide a function of the product.
  • the interface may be a functional and/or functional precursor composite material, the interface may be the region of the product where the composite provides a function of the product.
  • the term “particle” refers to a particle with any suitable size.
  • the particle has an average particle size of about 10 nm to about 150 ⁇ m in diameter, for example, ranging from about 10 nm to about 100 ⁇ m; about 25 nm to about 100 ⁇ m; about 10 nm to about 50 ⁇ m; about 25 nm to about 50 ⁇ m; about 10 nm to about 25 ⁇ m; about 25 nm to about 25 ⁇ m; about 10 nm to about 10 ⁇ m; about 25 nm to about 10 ⁇ m; about 10 nm to about 5 ⁇ m; about 25 nm to about 5 ⁇ m; about 10 nm to about 2.5 ⁇ m; about 25 nm to about 2.5 ⁇ m; about 10 nm to about 500 nm; about 25 nm to about 500 nm; about 10 nm to about 250 nm; about 25 nm to about 250 nm; about 10 nm to about 100 nm; about 25
  • particle as used herein thus includes “nanoparticle,” which is considered herein to be a particle having a diameter less than about 1000 nm, and “microparticle,” considered herein to be a particle having a diameter ranging from about 1 ⁇ m to about 1000 ⁇ m.
  • the particles described herein can be any shape, including generally spherical.
  • coating refers to a substantially homogenous layer (2D or 3D) or region within or on a product.
  • the term “functional coating” or “functional precursor coating” refers to a substantially homogenous layer (2D or 3D) or region of one or more functional and/or functional precursor components within or on a functional and/or functional precursor product.
  • the coating is a substantially homogenous layer (2D or 3D) of one or more functional and/or functional precursor components at or is an interface of the product.
  • the coating of functional and/or functional precursor component(s) may be layered on a polymer (e.g. matrix or scaffold) but the coating (e.g. nanoparticles or a distinct polymer coating of functional and/or functional precursor components) itself is not per se distributed within (e.g. incorporated in) the polymer.
  • graded refers to the presence of a concentration gradient of one or more components.
  • a concentration gradient of one or more functional and/or functional precursor components where the highest concentration of one or more of the functional and/or functional precursor components is at an interface of a product.
  • the components of a concentration gradient are distributed within a polymer (e.g. matrix or scaffold) of the product and such non-homogenous graded functional and/or functional precursor material may exhibit changes in microstructures and/or composition through different regions of the product.
  • the concentration gradient of a given component may change uniformly or change from shallow to steeper gradients (and vice-versa) through different regions of a product.
  • the term “composite” refers to a material made from two or more different components having different physical and/or chemical properties that, when combined, produce a material with characteristics different from the individual components themselves.
  • the individual components remain as individual components within the product.
  • the functional and/or functional precursor products may have regions (e.g. functional and/or functional precursor interface) or phases of one or more functional and/or functional precursor components that are not phase separated from a polymer (e.g. matrix or scaffold), and that are not distributed in a polymer as a concentration gradient.
  • the functional and/or functional precursor products may have regions (e.g.
  • functional and/or functional precursor interface or phases of one or more functional and/or functional precursor components at a functional interface that are not phase separated from a polymer (e.g. matrix or scaffold), and that are not distributed in a polymer as a concentration gradient.
  • composite concentrations and distributions of functional and/or functional precursor components are substantially the same as the starting composition of components prior to polymerization of a polymerizable component (e.g. resin) to form the polymer (e.g. matrix or scaffold) of the product.
  • the term “functional group” refers to a specific group of atoms that has its own characteristic properties, regardless of the other atoms present in a compound. Common examples are alkenes, alkynes, alcohols, amines, amides, carboxylic acids, ketones, esters, epoxides, and ethers.
  • the method is directed to making a polymeric product.
  • the polymeric product can be a functional product, a functional precursor product, or a combination of a functional and functional precursor product.
  • the method described herein may be used in vat polymerization 3D printing. Examples of vat polymerization 3D printing are stereolithography and digital light processing ( FIG. 23 ).
  • the method for making a product comprises a) combining at least one first polymerizable component and at least one second polymerizable component to form a composition; and b) polymerizing the at least one first polymerizable component to form at least one first polymer structure, wherein at least two phases are formed from the at least one first polymer structure and the at least one second polymerizable component, and wherein the product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product.
  • the method may further comprise c) polymerizing the at least one second polymerizable component to form at least one second polymer.
  • the method described herein is capable of controlling the placement/positioning of components(s) and/or polymer(s) (e.g. spatial positioning, spatially controlled positioning, etc.).
  • the method may provide selective positioning of component(s) and/or polymer(s) in a product (e.g. 2D or 3D structure). Therefore, the product may be designed such that specifically selected region(s) have one type of functionality and other region(s) have other type(s) of functionality.
  • a method can provide spatially controlled functionality in the product.
  • the selected region(s) and unselected region(s) are near, adjacent, and/or coupled to each other.
  • the first polymer(s) in the selected region(s) and the second polymer(s) in the unselected region(s) are near, adjacent, and/or coupled to each other.
  • the method described herein includes orthogonal polymerization, different rates of polymerization, and/or thermodynamic miscibility.
  • each of the polymerization reactions proceed via different mechanisms.
  • a mechanism of a polymerization reaction of the at least one first polymerizable component is different from a mechanism of a polymerization reaction of the at least one second polymerizable component.
  • Other embodiments may include as follows: a sequence of chemical reaction(s) of converting the at least one first polymerizable component (e.g. at least one first monomer and/or at least one first cross-linking agent) to the at least one first polymer, which differs from a sequence of chemical reaction(s) of converting the at least one second polymerizable component (e.g.
  • the chemical reaction(s) may include, for example, radical polymerization (e.g. involves the transfer of a radical from an initiator or building block to another monomer/cross-linking agent), cationic polymerization (e.g. involves the transfer of charge from a cationic initiator or building block to another monomer/cross-linking agent), and thermal polymerization (e.g. involves the addition of two or more molecules to form a larger molecule and eventually a polymer).
  • radical polymerization e.g. involves the transfer of a radical from an initiator or building block to another monomer/cross-linking agent
  • cationic polymerization e.g. involves the transfer of charge from a cationic initiator or building block to another monomer/cross-linking agent
  • thermal polymerization e.g. involves the addition of two or more molecules to form a larger molecule and eventually a polymer.
  • each of the polymerization reactions may proceed via different rates.
  • the rate of polymerizing the at least one first polymerizable component to form at least one first polymer is faster or slower than the rate of polymerizing the at least one second polymerizable component to form at least one second polymer.
  • certain monomer(s) that undergo radical polymerization may form polymers at a faster rate than other monomer(s) that undergo cationic polymerization.
  • (meth)acrylate-based monomers via radical polymerization may form polymers at a faster rate than epoxides via cationic polymerization.
  • Different polymerization rates can also occur within the same mechanism of polymerization (e.g. radical polymerization).
  • acrylates tend to be more reactive in a radical polymerization reaction compared to a radical polymerization reaction with (meth)acrylates.
  • polymerization rates can increase with increasing monomer functionality, for example, from mono- to di- to tri-functional groups.
  • the order of polymerization rates from fastest to slowest is tri-functionalized acrylates>di-functionalized acrylates>mono-functionalized acrylates>(meth)acrylates>epoxides.
  • the at least one first and the at least one second polymerizable components may be selected from monomer(s)/crosslinker(s) of these categories.
  • each of the polymerization reactions may affect the thermodynamic miscibility.
  • thermodynamic miscibility of the at least one first polymer is different from thermodynamic miscibility of the at least one second polymer.
  • the at least one first polymerizable component e.g. a first monomer and/or a first cross-linking agent
  • the molecular weight increases causing the entropy of mixing to be reduced which decreases the miscibility of the at least one second polymerizable component (e.g.
  • phase separation can depend on the solubility and balance of intermolecular forces between each component (each of the first and second monomer(s)/cross-linking agent(s)).
  • Incompatible functional groups in the polymerizable components can affect thermodynamic miscibility, such as polar vs. non-polar, steric vs. non-steric, aliphatic vs. aromatic, aliphatic vs. inorganic, can, for example, influence the solubility and degree of phase separation.
  • the composition has at least one first polymerizable component and at least one second polymerizable component.
  • the composition is a substantially homogeneous composition.
  • the substantially homogeneous composition is a substantially homogeneous mixture.
  • Polymerization may be achieved via initiation of polymerization in selected region(s) of the composition (e.g. mixture) having at least one polymerizable component and at least one second polymerizable component, whereby such polymerization can induce phase separation.
  • polymerization occurs in the selected region(s) to form a first polymer(s) and the unselected region(s) has the second polymerizable component(s).
  • There may be some first polymerizable component(s) in the unselected region(s) or some second polymerizable component(s) in the selected region(s).
  • the at least one polymerizable component and at least one second polymerizable component may be contained in, for example, as reservoir prior to polymerization of the selected region(s).
  • the polymerizing in b) and/or c) may comprise photopolymerization (e.g. photoinduced polymerization).
  • the at least one first polymerizable component has at least one first monomer and/or at least one first cross-linking agent.
  • the at least one second polymerizable component has at least one second monomer and/or at least one second cross-linking agent.
  • the composition further comprises at least one photoinitiator. Polymerization may also occur via free-radical polymerization without a photoinitiator.
  • the polymerizing may be achieved by exposing the composition (e.g. substantially homogeneous composition or substantially homogeneous mixture) to a radiation and/or a heat source (e.g. light or heat) capable of initiating polymerization of the at least one first polymerizable component.
  • a radiation and/or heat source e.g. light or heat
  • the radiation and/or heat source may be selected from a UV-Vis source, a laser, an electron beam, a gamma-radiation, an IR (heat) source, LED, microwave radiation, plasma and thermal treatment.
  • the polymerizing may be achieved by exposing the at least one first polymer and the at least one second polymerizable component to a radiation and/or a heat source capable of initiating polymerization of the at least one second polymerizable component.
  • the radiation and/or heat source may be selected from a UV-Vis source, a laser, an electron beam, a gamma-radiation, an IR (heat) source, LED, microwave radiation, plasma and thermal treatment. Therefore, polymerization is generally photopolymerization and/or thermal polymerization.
  • polymerization of selected regions of the composition is done using light and/or heat.
  • the polymerizable component(s) are selectively irradiated at a certain wavelength such that one type of polymerizable component polymerizes as opposed to another type.
  • irradiating the composition e.g.
  • substantially homogeneous composition or substantially homogeneous mixture with a light comprising at least one wavelength in a range of from about 250 to about 800 nm, so as to polymerize the irradiated portion of the mixture, thereby providing polymerized and unpolymerized regions to form an intermediate structure.
  • the intermediate structure is designed to have region(s) without the polymer (e.g. spaces, holes, apertures, depressions, pores, etc.) or having less polymer.
  • the intermediate structure is designed such that the patterned light and pre-selected structure causes the second polymerizable component(s) that have a slower polymerization rate, orthogonal reactivity, and/or lower solubility to diffuse towards unilluminated regions and to be spatially confined to “spaces” or certain regions within or between the intermediate product's structure, formed from the polymerization of the first polymerizable component.
  • layers of hexagons ( FIG. 27 a )) with support bridges 3D printed with the first polymerizable component are spaced such that the second polymerizable component and/or first component(s) (e.g.
  • This is in contrast to a structure, such as a solid rectangular prism that is not printed/illuminated to have spaces or regions where the second polymerizable or functional material component can be confined as it is formed and phase separates.
  • Another example includes the diffusion of the second polymerizable component to be confined within closed regions of the 3D printed structure (e.g. closed filled cubes).
  • the phase separation and architecture of the final 3D printed structure is defined by the kinetics and/or mechanisms of polymerization and/or thermodynamic miscibility of the components and the patterned illumination.
  • a second stage UV or thermal cure is used to polymerize the second polymerizable component that is formed by an orthogonal polymerization mechanism, for example, not photopolymerized by the 405 nm laser of the 3D printer.
  • the second stage UV or thermal cure polymerizes the second polymerizable component in regions that were not illuminated by the patterned light, but contain the second polymerizable component due to an additional infiltration step or due to phase separation during 3D printing.
  • the irradiated portion may be patterned through, for example, by a direct writing application of light, or by interference, nanoimprint, or diffraction gradient lithography, or by stereolithography, holography, or digital light projection (DLP).
  • DLP digital light projection
  • Patterned light is understood to include micro-patterned light.
  • a variable pattern and/or a pattern that is held constant over time may be used (e.g. fixed pattern). If variable, each irradiating step may be any suitable time or duration depending on factors such as the intensity of the irradiation, the rate of polymerization, etc.
  • the method provides selective positioning/placement of component(s) and/or polymer(s) in a product (e.g. 2D or 3D product).
  • the polymerization may be achieved via 3D printing and more particularly by vat polymerization 3D printing methods.
  • the 3D printing uses photoactivation and may be selected from stereolithographic (SLA) printing, digital light processing (DLP), and volumetric printing.
  • SLA stereolithographic
  • DLP digital light processing
  • the polymerizing in b) is photopolymerization
  • the polymerizing in c) is photopolymerization and/or thermal polymerization.
  • the composition e.g.
  • substantially homogeneous composition or substantially homogeneous mixture is irradiated with patterned light, whereby the at least one first polymerizable component polymerizes to form the 3D printed structure having the at least one first polymer and a separate phase of at least one second polymerizable monomer, which diffused away from region of the at least one first polymer.
  • the irradiation of the composition can define the 3D printed structure.
  • shorter irradiation time e.g. shorter laser time
  • Shorter wavelength may refer to a light source with a lower wavelength, such as in the 300 nm range as opposed to the 405 nm laser of a 3D printer.
  • the monomers of the second polymerizable component phase separate into spaces and are confined in such spaces.
  • a second stage UV cure (lower wavelength than the 405 nm laser) is used after the 3D part is printed in order to completely polymerize the second polymerizable component and form the two polymers (e.g. solid phases).
  • the 3D printed structure may be irradiated or heated with patterned light or heat to polymerize the at least one second polymerizable component (in the areas or volumes of the 3D printed structure, having a majority of the second polymerizable component) to the at least one second polymer to form the 3D printed product.
  • the resultant design used to irradiate or heat the 3D printed structure with patterned light or heat provided a continuity (e.g. the phases are near/adjacent to one another) in the 3D printed product.
  • a continuity e.g. the phases are near/adjacent to one another
  • (1) shows a substantially homogeneous resin mixture prior to photopolymerization
  • (2) shows the first polymerizable component (black) separate from the second polymerizable component (grey)
  • (3) shows selective photopolymerization of the mixture with patterned light to polymerize the first polymerizable component to form a first polymer (black) without polymerizing the second polymerizable component (grey)
  • (4) shows that the second polymerizable component (grey) has subsequently been polymerized to form a second polymer
  • (5) shows a brick-and-mortar type structure of a 3D printed product.
  • the first polymerizable component there is a higher concentration of the first polymerizable component compared to the second polymerizable component and the first polymerizable component polymerizes at a faster rate than the second polymerizable component based on the selected patterned light.
  • An example of the method shown in FIG. 24 is a holographic PIPS. The methods described herein can be used to build a bio-inspired pattern of materials at the micron-scale. In other examples, when the composition is initiated using a 405 nm laser, the first polymerizable component(s) has a faster polymerization rate compared to the second polymerizable component(s).
  • the second polymerizable component(s) is only polymerized with a lower wavelength UV light cure (second stage UV cure).
  • Selective photopolymerization of the at least one first polymerizable component to form the at least one first polymer which can result in the at least one second polymerizable component (e.g. second monomer(s) and/or second cross-linking agent(s)) phase separating and/or diffusing away from the first polymer, which is referred to as polymerization induced phase separation, PIPS, FIG. 24 .
  • the at least one second polymerizable component e.g. second monomer(s) and/or second cross-linking agent(s) phase separating and/or diffusing away from the first polymer, which is referred to as polymerization induced phase separation, PIPS, FIG. 24 .
  • PIPS polymerization induced phase separation
  • the composition (e.g. substantially homogeneous composition or substantially homogeneous mixture) of the at least one first polymerizable component and the at least one second polymerizable component is irradiated with patterned light to cause the at least one second polymerizable component (e.g. second monomer(s) and/or second cross-linking agent(s)), that has a slower polymerization rate, orthogonal reactivity, and/or lower solubility, to diffuse towards unilluminated regions of the 3D printed structure of the at least one first polymer, and to be spatially confined to “spaces” or certain regions (e.g. varying shapes) within or between the 3D printed structure of the faster polymerizing first polymerizable component (e.g.
  • the at least one second polymerizable component e.g. second monomer(s) and/or second cross-linking agent(s)
  • the at least one second polymerizable component e.g. second monomer(s) and/or second cross-linking agent(
  • the composition e.g. substantially homogeneous composition or substantially homogeneous mixture
  • the at least one first polymerizable component and the at least one second polymerizable component is irradiated with patterned light to cause the at least one second polymerizable component (e.g. second monomer(s) and/or second cross-linking agent(s)), that has a slower polymerization rate, orthogonal reactivity, and/or lower solubility, to diffuse towards unilluminated regions of the 3D printed structure of the at least one first polymer, and to be confined within “spaces” or certain regions (e.g.
  • the 3D printed structure is irradiated or heated (e.g. thermal or UV curing) such that the at least one second polymerizable component forms the at least one second polymer. See for example, FIG. 25 showing spatially controlled position of polymers.
  • first polymerizable component e.g. first monomer(s) and/or first cross-linking agent(s)
  • the 3D printed structure is irradiated or heated (e.g. thermal or UV curing) such that the at least one second polymerizable component forms the at least one second polymer. See for example, FIG. 25 showing spatially controlled position of polymers.
  • FIG. 25 showing spatially controlled position of polymers.
  • FIG. 25 (1) shows a design print file for a 3D product with microscale patterns consisting of illuminated (black) and masked (white) areas (image excludes support structures that may be needed in between the layers), (2) shows vat polymerization of substantially homogeneous resin mixture using micro-patterned light motif, wherein the mixture has a first polymerizable component and a second polymerizable component, and (3) shows the 3D printed product with the first polymer (black) and the second polymer (grey).
  • the method comprises combining a first polymerizable component(s) and a second polymerizable component(s).
  • the first polymerizable component(s) comprises monomer(s) and/or crosslinking agent(s), and a photoinitiator(s) in suitable amounts to provide the desired optimal properties.
  • the second polymerizable component(s) comprises thermal curable monomer(s) and/or crosslinking agent(s) in suitable amounts to provide the desired optimal properties.
  • the ratio of first polymerizable and second polymerizable component(s) was varied to optimize the phase separation and physical properties.
  • the first polymerizable component(s) and second polymerizable component(s) were combined to form a composition (e.g.
  • the mixture was irradiated (e.g. using a desired pattern) to polymerize the first polymerizable component(s), forming a 3D-printed polymer product having spaces or closed regions that confine, mostly, the second polymerizable component(s).
  • the second polymerizable component(s) are polymerized via thermal or UV curing.
  • phase separation occurs due to orthogonal polymerization mechanisms and/or thermodynamic miscibility of the first polymerizable component(s) and second polymerizable component(s).
  • the final product comprises alternating “hard” and “soft” polymers from the first polymerizable component and the second polymerizable component.
  • the method comprises combining a “hard” polymer resin and a “soft” polymerizable resin.
  • the “hard” polymer resin has (meth)acrylate monomer(s), di(meth)acrylate crosslinker(s), and a photoinitiator(s) in suitable amounts to provide the desired optimal mechanical properties of a “hard” polymer.
  • the “soft” polymer resin has epoxide(s) resin and amine(s) resin in suitable amounts to provide the desired optimal mechanical properties of a “soft” polymer.
  • the ratio of “hard” to “soft” polymer resins was varied to optimize the phase separation and mechanical properties.
  • the combination of “hard” and “soft” polymer resins were mixed to form a composition (e.g.
  • substantially homogeneous composition or substantially homogeneous mixture The mixture was irradiated (e.g. using a desired pattern) to polymerize the “hard” polymer resin, forming a “hard” polymer product (e.g. 3D-printed polymer product) having regions that are substantially free of the “hard” polymer (e.g. spaces) but including the “soft” polymer resin.
  • the “hard” polymer product was heated (e.g. thermally cured) and/or irradiated (e.g. UV cured).
  • the final product comprises both “soft” and “hard” polymers.
  • the method comprises combining a “hard” polymer resin and a “soft” polymerizable resin.
  • the “hard” polymer resin has (meth)acrylate monomer(s), di(meth)acrylate crosslinker(s), and a photoinitiator(s) in suitable amounts to provide the desired optimal mechanical properties of a “hard” polymer.
  • the “soft” polymer resin has epoxide(s) resin and amine(s) resin in suitable amounts to provide the desired optimal mechanical properties of a “soft” polymer.
  • the ratio of “hard” to “soft” polymer resins was varied to optimize the phase separation and mechanical properties.
  • the combination of “hard” and “soft” polymer resins were mixed to form a composition (e.g.
  • substantially homogeneous composition or substantially homogeneous mixture The mixture was irradiated (e.g. using a desired pattern) to polymerize the “hard” polymer resin, forming a “hard” polymer product (e.g. 3D-printed polymer product) having closed regions that are substantially free of the “hard” polymer (e.g. spaces) but confine the “soft” polymer resin (e.g. resin filled closed regions).
  • the “hard” polymer product having the confined “soft” polymer resin was heated (e.g. thermally cured) and/or irradiated (e.g. UV cured).
  • the final product comprises both “soft” and “hard” polymers.
  • the method comprises combining a first polymerizable component(s) and a second polymerizable component(s).
  • the first polymerizable component(s) comprise monomer(s) and/or cross-linking agent(s), and a photoinitiator(s) in suitable amounts to provide the desired optimal properties.
  • the second polymerizable component(s) comprises monomer(s) and/or crosslinker(s), and photoinitiator(s) in suitable amounts to provide the desired optimal properties.
  • the ratio of the first polymerizable and second polymerizable components was varied to optimize the phase separation and physical properties.
  • the first polymerizable component(s) and second polymerizable component(s) were combined to form a composition (e.g.
  • the mixture was irradiated (e.g. using a desired pattern) to polymerize the first polymerizable component polymer resin, forming a 3D-printed polymer product having closed regions that confine, mostly, the second polymerizable component(s).
  • the second polymerizable component are polymerized via thermal or UV curing.
  • phase separation occurs due to orthogonal polymerization mechanisms, different rates of polymerization, and/or thermodynamic miscibility of the first polymerizable component(s) and second polymerizable component(s).
  • the final product comprises alternating “hard” and “soft” polymers from the first polymerizable component(s) and the second polymerizable component(s).
  • the method comprises combining a “soft” polymer resin and a “hard” polymerizable resin.
  • the “soft” polymer resin has (meth)acrylate monomer(s), di(meth)acrylate crosslinker(s), and a photoinitiator(s) in suitable amounts to provide the desired optimal mechanical properties of a “soft” polymer.
  • the “hard” polymer resin has epoxide(s) resin and amine(s) resin in suitable amounts to provide the desired optimal mechanical properties of a “hard” polymer.
  • the ratio of “soft” to “hard” polymer resins was varied to optimize the phase separation and mechanical properties.
  • the combination of “soft” and “hard” polymer resins were mixed to form a composition (e.g.
  • substantially homogeneous composition or substantially homogeneous mixture The mixture was irradiated (e.g. using a desired pattern) to polymerize the “soft” polymer resin, forming a “soft” polymer product (e.g. 3D-printed polymer product) having closed regions that confine mostly “hard” polymer resin and some “soft” polymer resin (e.g. resin filled closed regions).
  • the “soft” polymer product having the confined “hard” polymer resin and some “soft” polymer resin was heated (e.g. thermally cured) and/or irradiated (e.g. UV cured).
  • the final product comprises both “soft” and “hard” polymers.
  • the method comprises combining a “hard” polymer resin and a “soft” polymerizable resin.
  • the “hard” polymer resin has (meth)acrylate monomer(s), and di(meth)acrylate crosslinker(s), one or both of which contains an epoxide functional group, and a photoinitiator(s) in suitable amounts to provide the desired optimal mechanical properties of a “hard” polymer.
  • the “soft” polymer resin has epoxide(s) resin (e.g. UV curable) or amine(s) resin (thermal curable) and a cationic initiator in suitable amounts to provide the desired optimal mechanical properties of a “soft” polymer.
  • the ratio of “hard” to “soft” polymer resins was varied to optimize the phase separation and mechanical properties.
  • the combination of “hard” and “soft” polymer resins were mixed to form a composition (e.g. substantially homogeneous composition or substantially homogeneous mixture).
  • the mixture was irradiated (e.g. using a desired pattern) to polymerize the “hard” polymer resin, forming a “hard” polymer product (e.g. 3D-printed polymer product) having regions that include the “soft” polymer resin (e.g. filled regions).
  • the “hard” polymer product having the “soft” polymer resin was heated (e.g. thermally cured) and/or irradiated (e.g. UV cured) to cause the pendent epoxide functional group of the 3D printed “hard” polymer to polymerize with the “soft” resin.
  • the final product comprises both “soft” and “hard” polymers.
  • the method for making a product comprises a) combining at least one first polymerizable component and at least one second polymerizable component to form a composition; b) polymerizing the at least one first polymerizable component to form at least one first polymer structure, wherein at least two phases are formed from the at least one first polymer structure and the at least one second polymerizable component, and c) polymerizing the at least one second polymerizable component to form at least one second polymer, and wherein the product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product.
  • the first polymer(s) may have at least one functional group that, in c), reacts with the second polymerizable component(s), which polymerizes the second polymerizable component(s) to the second polymer(s), and/or reacts with the second polymer(s).
  • the first polymer(s) are bonded/tethered to the second polymer(s) and/or the second polymerizable component(s).
  • the method comprises combining a “hard” polymer resin, a “soft” polymerizable resin and a photoinitiator.
  • the “hard” polymer resin has (meth)acrylate monomer(s), and di(meth)acrylate crosslinker(s) in suitable amounts to provide the desired optimal mechanical properties of a “hard” polymer.
  • the “soft” polymer resin has (meth)acrylate monomer(s), and di(meth)acrylate crosslinker(s), with slower kinetics and/or incompatible functional groups, in suitable amounts to provide the desired optimal mechanical properties of a “soft” polymer.
  • the ratio of “hard” to “soft” polymer resins was varied to optimize the phase separation and mechanical properties.
  • compositions e.g. substantially homogeneous composition or substantially homogeneous mixture.
  • the mixture was irradiated (e.g. using a desired pattern) to polymerize the “hard” polymer resin, forming a “hard” polymer product (e.g. 3D-printed polymer product) having regions, whereby the “soft” polymer resin separates and diffuses to the regions in the “hard” polymer product.
  • Phase separation of the “soft” polymer resin into the regions in the “hard” polymer product may occur due to kinetics (e.g. slower photopolymerization) and/or incompatible groups (e.g. acrylates and methacrylates that are polar vs.
  • the “hard” polymer product having the “soft” polymer resin was heated (e.g. thermally cured) and/or irradiated (e.g. UV cured) to polymerize the “soft” resin.
  • the final product comprises both “soft” and “hard” polymers.
  • the method comprises combining a “hard” polymer resin, a “soft” polymerizable resin, a photoinitiator, a cationic photoinitiator, and a photosensitizer.
  • the “hard” polymer resin has (meth)acrylate monomer(s), and di(meth)acrylate crosslinker(s) in suitable amounts to provide the desired optimal mechanical properties of a “hard” polymer.
  • the “soft” polymer resin has epoxide monomer(s) and epoxide crosslinking agent(s) in suitable amounts to provide the desired optimal mechanical properties of a “soft” polymer.
  • the ratio of “hard” to “soft” polymer resins was varied to optimize the phase separation and mechanical properties.
  • compositions e.g. substantially homogeneous composition or substantially homogeneous mixture.
  • the mixture was irradiated (e.g. using a desired pattern) to polymerize the “hard” polymer resin, forming a “hard” polymer product (e.g. 3D-printed polymer product) having regions, whereby the “soft” polymer resin separates and diffuses to the regions in the “hard” polymer product.
  • Phase separation of the “soft” polymer resin into the regions in the “hard” polymer product may occur due to kinetics (e.g. slower photopolymerization) and/or incompatible groups (e.g. acrylates and methacrylates that are polar vs.
  • the “hard” polymer product having the “soft” polymer resin was heated (e.g. thermally cured) and/or irradiated (e.g. UV cured) to polymerize the “soft” resin.
  • the final product comprises both “soft” and “hard” polymers.
  • the phase separation and architecture of the final 3D printed product may be defined by the kinetics, mechanisms of polymerization, and/or thermodynamic miscibility of the components and the patterned illumination of the 3D structure.
  • the resulting unique structural motifs can create an overall product with different or improved physical/chemical properties. For example, alternating “hard” and “soft” phases (e.g. “hard” and “soft” polymers) improves the overall mechanical properties compared to similar structures of only the individual polymer.
  • Phase separated functional materials e.g. first polymer(s) and second polymer(s) allow certain regions to be conductive, responsive to external stimuli, etc.
  • the first polymer(s) e.g. formed from the first monomer(s) and/or the first cross-linking agent(s)
  • the second polymer(s) e.g. formed from the second monomer(s) and/or the second cross-linking agent(s)
  • the first polymer(s) formed from polymerizing the first polymerizable component(s) may have mechanical properties that are characterized as “hard” or “soft”, while the second polymer(s) formed from polymerizing the slower, orthogonal and/or lower soluble second polymerizable component(s) may have mechanical properties that are characterized to be the opposite of the first polymer(s); “soft” or “hard”.
  • a “hard” polymer may have the following mechanical properties: about 2000 to about 4000 MPa range in modulus of elasticity, about 40 to about 65 MPa range in tensile strength, and/or about 10 to about 25% range in elongation at break;
  • a “soft” polymer may have the following mechanical properties: about 0.5 to about 5.0 MPa range in tensile strength and/or about 45 to about 250% range in elongation at break.
  • first polymer(s) and the second polymer(s) may be nanomaterials, dyes/pigments, conductive, tolerant, piezoelectric, responsive to external stimuli, and/or different environmental conditions, etc.
  • External stimuli or environmental conditions can include temperature, pressure, surrounding environment (water or other chemicals), magnetic field, etc.
  • the method for making a product comprises a) polymerizing at least one first polymerizable component to form at least one first polymer structure; b) combining the at least one first polymer structure and at least one first component, and wherein the at least one first component comprises at least one functional component, at least one functional precursor component, or combinations thereof.
  • the method further comprises c) polymerizing the at least one first component to form at least one second polymer, wherein the at least one first component comprises at least one second polymerizable component and wherein the product comprises the at least one second polymer and at least one first polymer structure.
  • the first polymer structure is a structure including space(s)/region(s) containing the first component(s).
  • the method comprises photopolymerization of the first polymerizable component to form a 3D printed intermediate structure while the first component(s) (e.g. polymer or second polymerizable component) is added in an additional step after 3D printing.
  • the first component(s) e.g. polymer or second polymerizable component
  • it may be polymerized using thermal polymerization, orthogonal polymerization mechanism, or by a second stage UV cure.
  • the 3D structure formed from the first polymerizable component contains spaces/holes. The spaces in the 3D printed structure were filled by either submerging the structure in the first component(s) or by capillary action and then thermally or UV cured if the second polymerizable component(s).
  • the final product comprises both “soft” and “hard” polymers with the “soft” polymer infiltrated into the “hard” 3D printed polymer.
  • the method comprises combining (meth)acrylate monomer(s), di(meth)acrylate crosslinker(s) and a photoinitiator in suitable amounts to provide the desired optimal mechanical properties of a “hard” polymer. The mixture was irradiated (e.g. using a desired pattern) to polymerize the “hard” polymer resin, forming a “hard” polymer product (e.g. 3D-printed polymer product) having regions (e.g.
  • a “soft” polymer resin having epoxide(s) resin and amine(s) resin in suitable amounts to provide the desired optimal mechanical properties of a “soft” polymer, was made.
  • the “hard” polymer product was combined (e.g. submerging, immersing, capillary action, etc.) with the “soft” polymer resin, whereby the “soft” polymer resin fills the spaces in the “hard” polymer product and then heated (e.g. thermally cured) and/or irradiated (e.g. UV cured) to to polymerize the “soft” resin.
  • the final product comprises both “soft” and “hard” polymers.
  • the method comprises combining the first polymerizable component to form the 3D printed structure and a first component(s) to phase separate, wherein the first component(s) is a polymer or derivative thereof.
  • the first polymerizable component comprises monomer(s) and/or crosslinking agent(s), and a photoinitiator(s) in suitable amounts to provide the desired optimal mechanical properties.
  • the first component(s) e.g. linear polymer, small molecule, etc.
  • phase due to thermodynamic miscibility of the first polymerizable component and the at least one first component(s).
  • the ratio of first polymerizable component(s) and first component(s) was varied to optimize the phase separation and desired resulting properties.
  • the first polymerizable component(s) and first component(s) were combined to form a composition (e.g. substantially homogeneous composition or substantially homogeneous mixture).
  • the mixture was irradiated (e.g. using a desired pattern) to polymerize the first polymerizable component, forming a 3D-printed polymer product in which the first component(s) is either confined within the structure and phase separated out of the spaces or phase separated out of the 3D structure and into the spaces.
  • the polymerizing in a), b) or c) may be performed for a time period sufficient for the polymerizable component(s) to substantially polymerize (e.g. solidify or reach a substantial gel-point), which will depend on the type of polymerizable component(s).
  • a time period sufficient for the polymerizable component(s) to substantially polymerize (e.g. solidify or reach a substantial gel-point), which will depend on the type of polymerizable component(s).
  • One skilled in the art would be able to determine the time period.
  • time periods are selected such that at least about 15% of the polymerizable component(s) convert to polymer(s), or at least about 30% of the polymerizable component(s) convert to polymer(s), or at least about 40% of the polymerizable component(s) convert to polymer(s), or at least about 50% of the polymerizable component(s) convert to polymer(s), or at least about 60% of the polymerizable component(s) convert to polymer(s), or about 40% to about 60% of the polymerizable component(s) convert to polymer(s). These percentages are based on the total weight of the at least one polymerizable component. In typical embodiments, there is sufficient polymerization for the polymerizable component(s) to generate, for example, a 3D-product.
  • any suitable amount can be used.
  • One embodiment includes from about 10% to about 99% by weight based on the weight of the homogeneous mixture. In some embodiments, the amount is from about 20% to about 99% by weight, from about 30% to about 99% by weight, from about 40% to about 99% by weight, from about 50% to about 99% by weight, from about 60% to about 99% by weight, from about 70% to about 99% by weight, or from about 80% to about 99% by weight based on the weight of the homogeneous mixture.
  • the product may be any suitable structure/object.
  • the product may be a 3D- or 2D-product.
  • the product may have one or more phases.
  • the product is a film or a 3D-product.
  • the product may have any desired geometry (e.g. shape).
  • Various 3D structures and functional high aspect ratio coatings and functional patterns in devices such as sensors, optoelectronic devices, solar cells, electrodes, RFID tags, antennas, electroluminescent devices, power sources and connectors for circuit boards may be fabricated.
  • the product may have at least one functional property selected from the group consisting of chemical properties, mechanical properties, magnetic properties, optical properties, insulating or protective properties (e.g.
  • the product is at least one of stretchable, flexible, lightweight, porous, conductive, non-conductive, surface durable, increased surface area, hydrophobic, biocompatible, anti-bacterial, mould resistant, wear-resistant, heat resistant, cold resistant, improved surface properties (antifouling), reduce flame retardancy, and combinations thereof.
  • the surface of the functional product e.g. coating itself, coating of 3D-product, etc.
  • the product is multifunctional and/or is a precursor product that is a precursor to a multifunctional product.
  • the product may be used for various applications, including metal/semiconductor, catalysis, sensing, electrochemical detection, EMI shielding, actuators and energy devices.
  • Other embodiments of commercial uses for the product include, for example, metamaterials with millimetre wave communication devices, objects embedded with self-healing materials, 3D objects with responsive materials (ferrofluidics, piezoelectric materials, conductive channels, etc.) for soft robotics, shape recovery objects with controlled placement/positioning of actuation material, encryption or anti-counterfeiting with treatment of spatially controlled structures with fluorescent ink, and/or parts for structural electronics (sensors and energy devices) with spatially controlled placement/positioning of conductive material within an object.
  • the product is conductive.
  • the product may be selected to be any suitable conductivity.
  • it may have a conductivity (e.g. resistance) of at least about 1 ⁇ /cm; at least about 2 ⁇ /cm; at least about 5 ⁇ /cm; at least about 10 ⁇ /cm; at least about 15 ⁇ /cm; or at least about 20 ⁇ /cm.
  • the conductivity may be from about 1 to about 50 ⁇ /cm; from about 2 to about 50 ⁇ /cm; from about 5 to about 50 ⁇ /cm; from about 10 to about 50 ⁇ /cm; from about 15 to about 50 ⁇ /cm; from about 20 to about 50 ⁇ /cm; from about 1 to about 40 ⁇ /cm; from about 2 to about 40 ⁇ /cm; from about 5 to about 40 ⁇ /cm; from about 10 to about 40 ⁇ /cm; from about 15 to about 40 ⁇ /cm; from about 20 to about 40 ⁇ /cm; from about 1 to about 30 ⁇ /cm; from about 2 to about 30 ⁇ /cm; from about 5 to about 30 ⁇ /cm; from about 10 to about 30 ⁇ /cm; from about 15 to about 30 ⁇ /cm; from about 20 to about 30 ⁇ /cm; from about 1 to about 25 ⁇ /cm; from about 2 to about 25 ⁇ /cm; from about 5 to about 25
  • the method described herein can further comprise at least one first component.
  • the first component(s) comprises at least one functional component, at least one functional precursor component, or a combination thereof.
  • the first component(s) can be added to the composition (e.g. substantially homogeneous composition or substantially homogeneous mixture).
  • the method comprises converting the at least one functional precursor component into at least one second functional component.
  • the at least one second functional component is different from said at least one functional component.
  • the at least one second functional component is the same as the at least one functional component.
  • the converting may comprise sintering and/or pyrolyzing, for example, as described above.
  • the at least one functional precursor component is capable of being converted into at least one second functional component via sintering.
  • the sintering may be at least one of thermal sintering, UV-VIS radiation sintering, and laser sintering.
  • sintering may occur during or after printing.
  • the method may thus comprise an additional step of converting a metal precursor into a metal form which may thereafter be sintered.
  • the method further comprises sintering the product formed from b) or c), pyrolyzing the product formed from b) or c), or sintering and pyrolyzing the product formed from b) or c).
  • sintering is thermal sintering, UV-VIS radiation sintering, laser sintering or any combination thereof.
  • minimum thermal sintering temperatures are selected based on a minimum temperature for converting the functional precursor to the functional product.
  • Maximum thermal sintering temperatures may be selected based on a maximum temperature that the functional precursor and/or the functional product may be heated to without causing substantive decomposition or degradation.
  • the temperature ranges include, but are not limited thereto, from about 50° C. to about 300° C., or about 50° C. to about 280° C., or about 100° C. to about 280° C., or about 100° C. to about 270° C., or about 150° C. to about 280° C., or about 160° C. to about 270° C., or about 180° C. to about 250° C., or about 230° C. to about 250° C.
  • Thermal sintering may occur under air or under inert condition(s), such as nitrogen.
  • Thermal sintering may be performed for a time in ranges of about 15 minutes to about 180 minutes, or about 30 minutes to about 120 minutes, or about 45 minutes to about 60 minutes. In typical embodiments, sintering occurs under nitrogen with about 500 ppm oxygen. With respect to UV-VIS radiation sintering, sintering energies may range from about 1 J/cm 2 to about 30 J/cm 2 , or about 2 J/cm 2 to about 10 J/cm 2 , or about 2.5 J/cm 2 to about 5 J/cm 2 , or about 2.4 J/cm 2 to about 3.1 J/cm 2 .
  • the pulse widths are about 500 s to about 5000 s, or about 1000 s to about 4000 s, or about 2500 s to about 3000 s.
  • UV-VIS radiation sintering occurs under air.
  • the temperature ranges include, but are not limited thereto, from about 350° C. to about 1200° C., or about 400° C. to about 900° C., or about 600° C. to about 800° C., or about 700° C. to about 800° C.
  • Pyrolyzing may be performed for a time in a range of about 1 to about 60 minutes. Pyrolyzing may occur under air or under inert condition(s), such as nitrogen.
  • the first and second polymer(s) have a weight average molecular weight of about 10,000 to about 10,000,000, or about 10,000 to about 5,000 000, or about 10,000 to about 1,000,000, or about 50,000 to about 1,000,000, or about 50,000 to about 500,000. It is understood that the weight average molecular weight may approach infinity and includes cross-linked polymeric network(s).
  • each, independently, may comprise at least one monomer and/or at least one oligomer.
  • the at least one first and second polymerizable component(s) may comprise at least one liquid monomer and/or at least one liquid oligomer.
  • the at least one first polymerizable component and/or the at least one second polymerizable component comprises at least one resin.
  • Some examples include resins based on epoxies, vinyl ethers, acrylates, urethane-acrylates, methacrylates, acrylamides, thiol-ene based resins, styrene, siloxanes, silicones, and any functionalized derivatives thereof (e.g.
  • the at least one resin may comprise at least one commercial resin.
  • typical examples of the at least one resin comprises at least one commercial resin for 3D printing such as, and without being limited thereto, 3D printing via photoactivation (e.g. stereolithographic (SLA) printing or digital light processing (DLP)).
  • the at least one resin may comprise at least one acrylate based-resin.
  • the monomer resins may be elastomers or pre-ceramic polymers.
  • the monomers and oligomers are selected according to their physico-chemical and chemical properties, such as monomer viscosity and/or surface tension, and/or polymer elasticity and/or hardness, number of polymerizable groups, and according to the printing method and the polymerization reaction type, e.g., the radiation source or heat source of choice.
  • modulus value ranges of from about 0.1 MPa to about 8000 MPa.
  • the monomers are selected from acid containing monomers, acrylic monomers, amine containing monomers, cross-linking acrylic monomers, dual reactive acrylic monomers, epoxides/anhydrides/imides, fluorescent acrylic monomers, fluorinated acrylic monomers, high or low refractive index monomers, hydroxy containing monomers, mono and difunctional glycol oligomeric monomers, styrenic monomers, vinyl and ethenyl monomers.
  • the monomers can polymerize to yield conductive polymers such as polypyrole and polyaniline.
  • the at least one monomer is selected from dipentaerythnitol hexaacrylate (DPHA) and trimethylolpropane triacrylate (TMPTA).
  • the at least one oligomer is selected from the group consisting of acrylates and vinyl containing molecules.
  • the monomer can be any monomeric compound having a functional group, such as an activatable photopolymerizable group (photoinduced polymerization) that can propagate, for example, carbon-carbon, carbon-oxygen, carbon-nitrogen, or carbon-sulfur bond formation.
  • the monomer is selected from mono-functional monomers (e.g. monomers with one functional group). During polymerization, the radical of the monofunctional monomer is formed and it will react with other monomers present to form oligomers and polymers. The resultant oligomers and polymers can have different properties depending on its structure. Some monomers may be selected depending on their flexibility, viscosity, curing rate, reactivity or toxicity.
  • the monomer is polymerized to form a polyacrylate such as polymethylmethacrylate, an unsaturated polyester, a saturated polyester, a polyolefin (polyethylenes, polypropylenes, polybutylenes, and the like), an alkyl resin, an epoxy polymer, a polyamide, a polyimide, a polyetherimide, a polyamideimide, a polyesterimide, a polyesteramideimide, polyurethanes, polycarbonates, polystyrenes, polyphenols, polyvinylesters, polysilicones, polyacetals, cellulose acetates, polyvinylchlorides, polyvinylacetates, polyvinyl alcohols polysulfones, polyphenylsulfones, polyethersulfones, polyketones, polyetherketones, poyletheretherketones, polybenzimidazoles, polybenzoxazoles, polybenzthiazoles, polyfluorocarbones,
  • polyacrylates include polyisobornylacrylate, polyisobornylmethacrylate, polyethoxyethoxyethyl acrylate, poly-2-carboxyethylacrylate, polyethylhexylacrylate, poly-2-hydroxyethylacrylate, poly-2-phenoxylethylacrylate, poly-2-phenoxyethylmethacrylate, poly-2-ethylbutylmethacrylate, poly-9-anthracenylmethylmethacrylate, poly-4-chlorophenylacrylate, polycyclohexylacrylate, polydicyclopentenyloxyethyl acrylate, poly-2-(N,N-diethylamino)ethyl methacrylate, poly-dimethylaminoeopentyl acrylate, poly-caprolactone 2-(methacryloxy)ethylester, and polyfurfurylmethacrylate, poly(ethylene glycol)methacrylate, poly(
  • Monomers and oligomers that may be used include acrylic monomers such as monoacrylics, diacrylics, triacrylics, tetraacrylics, pentacrylics, etc.
  • examples of other monomers include ethyleneglycol methyl ether acrylate, N,N-diisobutyl-acrylamide, N-vinyl-pyrrolidone, (meth)acryloyl morpholine, 7-amino-3,7-dimethyloctyl, (meth) acrylate, isobutoxymethyl (meth) acrylamide, isobornyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl (meth)acrylate, ethyldiethylene glycol (meth)acrylate, t-octyl (meth)acrylamide, diacetone (meth) acrylamide, dimethylamin
  • epoxide monomers such as 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, bisphenol A diglycidyl ether, allyl glycidyl ether, bis[4-(glycidyloxy)phenyl]methane, 1,3-butadiene diepoxide, 1,4-butanediol diglycidyl ether, butyl glycidyl ether, tert-butyl glycidyl ether, 4-chlorophenyl glycidyl ether, cyclohexene oxide, dicyclopentadiene dioxide, 1,2,7,8-diepoxycyclooctane, 1,2,5,6-diepoxyoctane, styrene oxide, neopentyl glycol dilycidyl ether, glycidyl isopropyl ether
  • any suitable amount can be used depending on the desired functional and/or functional precursor product.
  • One embodiment includes from about 10% to about 99% by weight of the at least one monomer based on the weight of the composition.
  • the amount is from about 15% to about 90% by weight, from about 15% to about 85% by weight, from about 15% to about 80% by weight, from about 15% to about 75% by weight, from about 20% to about 90% by weight, from about 30% to about 90% by weight, from about 35% to about 90% by weight, from about 45% to about 90% by weight, from about 50% to about 90% by weight, from about 55% to about 90% by weight, from about 60% to about 90% by weight, from about 30% to about 80% by weight, from about 35% to about 80% by weight, from about 40% to about 80% by weight, from about 45% to about 80% by weight, or from about 50% to about 80% by weight based on the weight of the composition.
  • the amount of the at least one monomer that may be used in embodiments based on the weight of the at least one polymerizable component itself includes from about 1% to about 90% by weight of the at least one monomer. In some embodiments, the amount is from about 1% to about 85% by weight, from about 1% to about 80% by weight, from about 1% to about 75% by weight, from about 5% to about 90% by weight, from about 10% to about 90% by weight, from about 15% to about 90% by weight, from about 20% to about 90% by weight, from about 25% to about 90% by weight, from about 35% to about 90% by weight, from about 40% to about 90% by weight, from about 45% to about 90% by weight, from about 5% to about 80% by weight, from about 10% to about 80% by weight, from about 15% to about 80% by weight, from about 20% to about 80% by weight, or from about 50% to about 80% by weight based on the weight of the at least one polymerizable component.
  • cross-linking agent it may be included in the composition (e.g. substantially homogeneous composition or substantially homogeneous mixture).
  • Cross-linking agents may have one or more functional groups and, typically, have two or more functional groups (e.g. di-, tri-, tetra-, etc. functional cross-linking agents).
  • the functional groups may be present at both ends of the cross-linking agent, forming branched polymerization, whereby the cross-linking agent may react with two or more polymers.
  • a 2D product is formed with a monofunctional cross-linking agent and a 3D product is formed with a multifunctional cross-linking agent.
  • the morphology of a functional and/or functional precursor product may depend on the concentration (e.g. amount) of cross-linking agent.
  • concentration of the cross-linking agent may control the rate at which a polymer network forms.
  • the rate at which the monomers form polymer networks e.g. branched polymerization
  • High rates of polymer network formation may limit the diffusion of slower reacting or non-polymerizing components and provide more uniform compositions such as composites in certain regions (e.g. portions) of the product.
  • the morphology of the functional and/or functional precursor product can be a function of cross-linking agent concentrations in compositions (e.g. substantially homogeneous compositions or substantially homogeneous mixtures) containing non-polymerizing functional and/or functional precursor components.
  • the amount of functional and/or functional precursor component at the surface of the functional and/or functional precursor product decreases with increased concentration of cross-linking agent.
  • the concentration of functional and/or functional precursor component at the surface can determine the resistance value of the printed product.
  • the resistance of the functional and/or functional precursor component at the surface increases in view of the lower concentration of the functional and/or functional precursor component at the surface.
  • any suitable amount can be used depending on the desired functional and/or functional precursor product.
  • the amount of the at least one cross-linking agent can be used to tune the morphology of the functional and/or functional precursor product.
  • One embodiment includes from about 10% to about 99% mol based on the composition.
  • the amount is from about 80% to about 99% mol, from about 85% to about 99% mol, from about 90% to about 99% mol, from about 10% to about 80% mol, from about 10% to about 70% mol, from about 10% to about 60% mol, from about 10% to about 50% mol, from about 10% to about 40% mol, from about 10% to about 35% mol, from about 20% to about 80% mol, from about 25% to about 80% mol, from about 30% to about 80% mol, from about 35% to about 80% mol, from about 40% to about 80% mol, from about 45% to about 80% mol, from about 50% to about 80% mol, from about 55% to about 80% mol, from about 60% to about 80% mol, from about 65% to about 80% mol, from about 70% to about 80% mol, from about 35% to about 75% mol, from about 35% to about 70% mol, from about 35% to about 65% mol, from about 35% to about 60% mol, from about 3
  • any suitable amount can be used.
  • One embodiment includes from about 10% to about 99% by weight of the at least one cross-linking agent based on the weight of the homogeneous mixture.
  • the amount is from about 15% to about 90% by weight, from about 15% to about 85% by weight, from about 15% to about 80% by weight, from about 15% to about 75% by weight, from about 20% to about 90% by weight, from about 30% to about 90% by weight, from about 35% to about 90% by weight, from about 45% to about 90% by weight, from about 50% to about 90% by weight, from about 55% to about 90% by weight, from about 60% to about 90% by weight, from about 30% to about 80% by weight, from about 35% to about 80% by weight, from about 40% to about 80% by weight, from about 45% to about 80% by weight, or from about 50% to about 80% by weight based on the weight of the composition.
  • the amount of the at least one cross-linking agent that may be used in embodiments based on the weight of the at least one polymerizable component itself includes from about 10% to about 99% by weight of the at least one cross-linking agent.
  • the amount is from about 15% to about 90% by weight, from about 15% to about 85% by weight, from about 15% to about 80% by weight, from about 15% to about 75% by weight, from about 20% to about 90% by weight, from about 30% to about 90% by weight, from about 35% to about 90% by weight, from about 45% to about 90% by weight, from about 50% to about 90% by weight, from about 55% to about 90% by weight, from about 60% to about 90% by weight, from about 30% to about 80% by weight, from about 35% to about 80% by weight, from about 40% to about 80% by weight, from about 45% to about 80% by weight, or from about 50% to about 80% by weight based on the weight of the at least one polymerizable component (e.g. resin).
  • the cross-linking agent is a radical reactive cross-linking agent.
  • the radical reactive cross-linking agent include a methacrylic compound, an acrylic compound, a vinyl compound, and an allyl compound.
  • suitable cross-linking agents which can be used to form polyacrylates include 2,2-bis(4-methacryloxyphenyl)propane, 1,2-butanediol diacrylate, 1,4-butanediol diacrylate, ethylene glycol diacrylate, di(ethylene glycol) diacrylate, tetra(ethylene glycol) diacrylate, ethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,4-cyclohexanediol dimethacrylate, 1,10-decanediol dimethacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, dimethylpropanediol dimethacrylate, triethylene glycol dimethacrylate,
  • triacrylates which can be used to form polyacrylates include tris(2-hydroxyethyl)isocyanurate trimethacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate and pentaerythritol triacrylate.
  • tetracrylates include pentaerythritol tetraacrylate, di(trimethylolpropane) tetraacrylate, and ethoxylated pentaerythritol tetraacrylate.
  • pentaacrylates include dipentaerythritol pentaacrylate and pentaacrylate ester.
  • cross-linking agents include: ethylene glycol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, triethylene glycol diacrylate, tetraethylene glycoldi(meth)acrylate, tricyclodecanediyl-dimethylene di(meth)acrylate, tris(2-hydroxyethyl) isocyanurate di(meth)acrylate, tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, caprolactone modified tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, trimethylolpropane tri(meth) acrylate, EO modified trimethylolpropane tri(meth)acrylate, PO modified trimethylolpropane tri(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, both terminal (meth)acrylic acid adduct of bisphenol A
  • the radiation source employed for initiating the polymerization is selected based on the type of photoinitiator used.
  • the photoinitiator is a chemical compound that decomposes into free radicals when exposed to light but cationic photoinitiators may be used as well.
  • photoinitiators There are a number of photoinitiators known in the art.
  • suitable photoinitiators include, but are not limited to, ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate, 7-diethylamino-2-coumarin, acetophenone, p-tert-butyltrichloro acetophenone, chloro acetophenone, 2-2-diethoxy acetophenone, hydroxy acetophenone, 2,2-dimethoxy-2′-phenyl acetophenone, 2-amino acetophenone, dialkylamino acetophenone, benzil, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-2-methylpropane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane
  • One embodiment includes less than about 0.5% by weight of the at least one photoinitiator based on the weight of the homogeneous mixture. In some embodiments, the amount is less than about 0.4% by weight, less than about 0.3% by weight, or less than about 0.1% by weight based on the weight of the homogeneous mixture.
  • the amount of the at least one photoinitiator that may be used in embodiments based on the weight of the at least one polymerizable component itself includes less than about 3% by weight of the at least one photoinitiator. In some embodiments, the amount is less than about 3% by weight, less than about 1.8% by weight, less than about 1.5% by weight, or less than about 1% by weight based on the weight of based on the weight of the at least one polymerizable component (e.g. resin).
  • the photosensitizers are used to initiate polymerization (e.g. may initiate formation of free radicals from a photoinitiator).
  • a photoinitiator e.g. may initiate formation of free radicals from a photoinitiator.
  • photosensitizers known in the art. A skilled person would understand a suitable amount of photosensitizers that may be used to initiate a photopolymerization reaction.
  • suitable photosensitizers include, but are not limited to, isopropyl-9H-thioxanthen-9-one, anthracene, phenothiazine, perylene, thioxanthone, benzophenone, acetophenone, pyrene, acridinedione, boron-dipyrromethenes, curcumin, coumarin, etc.
  • the method may form more radicals causing a larger concentration of the monomers to polymerize quickly, forming a more fragile product.
  • fewer points of branching may result in a product with higher fragility.
  • An excess of cross-linking agent may also cause the monomer to gel quickly, creating an inelastic structure.
  • higher cross-linking agent percentages may provide products having greater tensile strength and lower cross-linking agent percentages may provide products having lower resistivities.
  • higher cross-linking agent percentages may provide products having greater tensile strength with graded and composite products and lower cross-linking agent percentages may provide products having lower resistivities with functionally coated phase separated products.
  • the ratios of the components of the at least one polymerizable component any suitable ratios can be used depending on the desired functional and/or functional precursor product.
  • the ratio of the at least one monomer to at least one cross-linking agent includes about 9:1 to about 0:10 based on % by weight.
  • the amount is about 9:1 to about 1:9 based on % by weight, about 8:2 to about 2:8 based on % by weight, about 7:3 to about 3:7 based on % by weight, about 6:4 to about 4:6 based on % by weight, about 5:5 to about 5:5 based on % by weight, about 4:6 to about 6:4 based on % by weight, about 3:7 to about 7:3 based on % by weight, about 2:8 to about 8:2 based on % by weight, or about 1:10 to about 9:1 based on % by weight.
  • the ratio of the at least one monomer to at least one cross-linking agent to at least one photoinitiator includes about 8.9:1:0.1 to about 0:9.9:0.1 based on % by weight.
  • the attractive and repulsive forces (hydrophobic/hydrophilic interactions) between components may be leveraged to control the placement of functional components.
  • the components When components have similar hydrophilic or hydrophobic properties, the components will have less of a driving force to phase separate upon polymerization. If the components differ in their hydrophobicity or hydrophilicity, the functional component will have a larger driving force to separate from the composition (e.g. substantially homogenous polymerizing monomer/cross-linking agent composition/mixture).
  • the resulting product may be used as a scaffold for receiving metallic functional components (e.g. through electroplating) and as barrier type coatings (e.g. hydrophobic), dielectrics or insulating material, and may be selected for the desired flexibility and strength needed in the final product.
  • the at least one first component can separate and migrate towards a region where the concentration of the at least one first polymerizable component is greater (which may be slowly decreasing with polymerization) and the at least one second polymerizable component is greater and forms a composite coating of, mostly, the first component and the at least one second polymerizable component.
  • the at least one first component can separate and migrate towards a region where the concentration of the at least one second polymerizable component is greater and forms a coating of the first component.
  • the product comprises at least about 0.1% by weight of the at least one first component, or at least about 1% by weight of the at least one first component, or at least about 3% by weight of the at least one first component, or at least about 5% by weight of the at least one first component, or at least about 7% by weight of the at least one first component, or at least about 10% by weight of the at least one first component, or at least about 15% by weight of the at least one first component, or at least about 20% by weight of the at least one first component, or at least about 25% by weight of the at least one first component, or at least about 30% by weight of the at least one first component, based on the total weight of the product.
  • the product comprises about 0.1 wt % to about 30 wt % by weight of the at least one first component, or about 3 wt % to about 25 wt % by weight of the at least one first component, or about 5 wt % to about 20 wt % by weight of the at least one first component, or about 5 wt % to about 15 wt % by weight of the at least one first component, based on the total weight of the product.
  • the product comprises a functional material.
  • the functional material may be a functionally graded material (FGM).
  • the FGM may be a functionally graded composite material (FGCM).
  • the at least one first component is substantially soluble in the at least one first and/or second polymerizable component(s) and is substantially insoluble when the first and/or second polymerizable component(s) polymerizes.
  • the at least one first component may be selected from the group consisting of functional monomers, functional polymers, metal precursors, carbon nanotubes (CNT), graphene, metal alloy precursors, metalloid precursors, and combinations thereof.
  • the at least one first component is at least one functional monomer.
  • the at least one functional monomer may be fluorinated monomers such as, and without being limited thereto, fluorinated methacrylates.
  • the fluorinated functional monomers may contribute hydrophobic properties to the functional product.
  • the at least one polymerizable component is selectively polymerized (e.g. temperature/wavelength used) without substantially polymerizing the at least one functional monomer such that, for example, the functional monomer and the at least one polymer form at least two phases.
  • the functional monomer may polymerize somewhat with the at least one first and/or second polymerizable component(s); however, at least two phases form.
  • the at least one first component may be at least one functional polymer such as, and without being limited thereto, PEG.
  • the at least one polymerizable component is polymerized such that, for example, the functional polymer and the at least one first and/or second polymerizable component(s) form at least two phases.
  • the at least one first component is selected from the group consisting of metal salts, metal coordination compounds, organometallic compounds, organometalloid compounds, and combinations thereof. In typical embodiments, the at least one first component is selected from the group consisting of metal salts, metalloid salts, and combinations thereof. In certain embodiments, the at least one first component is selected from the group consisting of metal carboxylates, metalloid carboxylates, and combinations thereof.
  • the metal carboxylates may comprise from 1 to 20 carbon atoms, from 6 to 15 carbon atoms, or from 8 to 12 carbon atoms.
  • the carboxylate group of the metal carboxylates may be an alkanoate.
  • Examples of the at least one first component is selected from the group consisting of metal formate, metal acetate, metal propionate, metal butyrate, metal pentanoate, metal hexanoate, metal heptanoate, metal ethylhexanoate, metal behenate, metal benzoate, metal oleate, metal octanoate, metal nonanoate, metal decanoate, metal neodecanoate, metal hexafluoroacetylacetonate, metal phenylacetate, metal isobutyrylacetate, metal benzoylacetate, metal pivalate metal oxalate and combinations thereof.
  • the metal ion may be selected from the group consisting of Li + , Na + , K + , Rb + , Cs + , Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Sc 3+ , Sc 2+ , Sc + , Y 3+ , Y 2+ , Y + , Ti 4+ , Ti 3+ , Ti 2+ , Zr 4+ , Zr 3+ , Zr 2+ , Hf 4+ , Hf 3+ , V 5+ , V 4+ , V 3+ , V 2+ , Nb 5+ , Nb 4+ , Nb 3+ , Nb 2+ , Ta 5+ , Ta 4+ , Ta 3+ , Ta 2+ , Cr 6+ , Cr 5+ , Cr 4+ , Cr 3+ , Cr 2+ , Cr + , Cr, Mo 6+ , Mo 5+ , Mo 4+ , Mo 4+ ,
  • the at least one first component used in the method may be selected amongst nanoparticles and/or microparticles of at least one first component described herein.
  • the nanoparticles and/or microparticles may be metal precursors such as metal ions, metal salts, metal oxides, and/or metal complexes which may be convertible to metal.
  • the at least one first component may be any suitable inorganic particle that can separate into at least two phases from the at least one polymer, including nanoparticles and/or microparticles.
  • the nanoparticles or microparticles are composed of a metal or combinations of metals selected from metals of Groups IIA, IIIA, IIIB, IVB, VB, VIB, VIIB, VIIIB, IB or IIB of block d of the Periodic Table of Elements.
  • said metallic nanoparticles or microparticles are selected from Ba, Al, Sc, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Y, Zr, Nb, Tc, Ru, Mo, Rh, W, Au, Pt, Pd, Ag, Mn, Co, Cd, Hf, Ta, Re, Os, Al, Sn, In, Ga, Ir, and combinations thereof.
  • said metallic nanoparticles or microparticles are selected from Ba, Al, Cu, Ni, Ag, Au, Pt, Pd, Al, Fe, Co, Ti, Zn, In, Sn, Ga and combinations thereof. In yet other embodiments, said metallic nanoparticles or microparticles are selected from Al, Cu, Ni, Ti, Zn, Ag, and combinations thereof.
  • said metallic nanoparticles or microparticles are selected from Ag, Cu, and Ag and Cu nanoparticles. In other embodiments, the metallic nanoparticles or microparticles are Ag nanoparticles.
  • the at least one first component is a metal precursor selected to be convertible in-situ into a metal by a chemical or electrochemical process. The metal precursor may also be reduced into corresponding metal by reduction of the metal precursor in the presence of a suitable photoinitiator and a radiation source. Thus, in some embodiments, the metal precursor is selected to be convertible into any one of the metals recited hereinabove. In some embodiments, the metal precursor is a salt form of any one metal recited hereinabove.
  • the metal salt is comprised of an inorganic or organic anion and an inorganic or organic cation.
  • the anion is inorganic.
  • inorganic anions include HO ⁇ , F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , NO 2 ⁇ , NO 3 ⁇ , ClO 4 ⁇ , SO 4 2 ⁇ , SO 3 ⁇ , PO 4 ⁇ and CO 3 2 ⁇ .
  • the anion is organic.
  • Non-limiting examples of organic anions include acetate (CH 3 COO ⁇ ), formate (HCOO ⁇ ), citrate (C 3 H 5 O(COO) 3 ⁇ 3 ) acetylacetonate, lactate (CH 3 CH(OH)COO ⁇ ), oxalate ((COO) 2 ⁇ 2 ) and any derivative of the aforementioned.
  • the metal salt is not a metal oxide.
  • the metal salt is a metal oxide.
  • the metal salt is a salt of copper.
  • Non-limiting examples of copper metal salts include copper formate, copper citrate, copper acetate, copper nitrate, copper acetylacetonate, copper perchlorate, copper chloride, copper sulfate, copper carbonate, copper hydroxide, copper sulfide or any other copper salt and the combinations thereof.
  • the metal salt is a salt of nickel.
  • nickel metal salts include nickel formate, nickel citrate, nickel acetate, nickel nitrate, nickel acetylacetonate, nickel perchlorate, nickel chloride, nickel sulfate, nickel carbonate, nickel hydroxide or any other nickel salts and the combinations thereof.
  • the metal salt is a salt of silver.
  • silver metal salts include silver carboxylates, silver lactate, silver nitrate, silver formate or any other silver salt and their mixtures.
  • silver carboxylates may be used and comprise a silver ion and an organic group containing a carboxylate group.
  • the carboxylate group may comprise from 1 to 20 carbon atoms, typically from 6 to 15 carbon atoms, more typically from 8 to 12 carbon atoms, for example 10 carbon atoms.
  • the carboxylate group is typically an alkanoate.
  • silver carboxylates are silver ethylhexanoate, silver neodecanoate, silver benzoate, silver phenylacetate, silver isobutyrylacetate, silver benzoylacetate, silver oxalate, silver pivalate and any combinations thereof.
  • silver neodecanoate is used.
  • the metal salt is selected from indium(II) acetate, indium(III) chloride, indium(III) nitrate; iron(II) chloride, iron(III) chloride, iron(II) acetate, gallium(III) acetylacetonate, gallium(II) chloride, gallium(II) chloride, gallium(II) nitrate; aluminum(III) chloride, aluminum(III) stearate; silver nitrate, silver chloride; dimethylzinc, diethylzinc, zinc chloride, tin(II) chloride, tin(IV) chloride, tin(II) acetylacetonate, tin(II) acetate; lead(II) acetate, lead(II) acetylacetonate, lead(II) chloride, lead(II) nitrate and PbS.
  • the at least one first component is selected from metal oxides such as those mentioned above, including nanoparticles and/or microparticles.
  • the metal oxides are selected from alumina, silica, barium titanate, transition metal oxides (e.g. zinc oxide, titanium oxide), and combinations thereof.
  • the at least one first component is selected from nanowires, microparticles, nanoparticles, or combinations thereof, including any of the suitable at least one first component mentioned herein.
  • the at least one first component comprises graphene.
  • the amount of the at least one first component may be any suitable amount.
  • the amount may be from about 0.1% to about 90% by weight based on the weight of the homogeneous mixture.
  • the amount of the at least one first component in the homogeneous mixture may be from about 0.1% to about 80% by weight, from about 0.1% to about 70% by weight, from about 0.1% to about 60% by weight, from about 0.1% to about 50% by weight, from about 0.1% to about 40% by weight, from about 0.1% to about 30% by weight, or from about 0.1% to about 20% by weight based on the weight of the homogeneous mixture.
  • additives may be added. Additives can be included, for example, to increase the solubility of the at least one first component in the at least one polymer component.
  • Various additives include, without being limited thereto, fillers, inhibitors, adhesion promoters, absorbers, dyes, pigments, anti-oxidants, carrier vehicles, heat stabilizers, flame retardants, thixotropic agents, flow control additives, dispersants, or combinations thereof.
  • extending fillers, reinforcing fillers, dispersants, or combinations thereof are added.
  • the additives can be microparticles or nanoparticles.
  • a polymeric product made by the method described herein, wherein the product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product.
  • the method can provide spatially controlled functionality in a product.
  • Such products may include, for example, improved mechanical or functional properties, controlled functionality with one step (3D printing), less material waste, less time consuming fabrication.
  • a product comprises i) at least one first polymer structure comprising at least one first polymer; and ii) at least one second polymerizable component, wherein the product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product.
  • a product comprises i) at least one first polymer structure comprising at least one first polymer; and ii) at least one first component, wherein the product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product
  • a product comprises i) at least one first polymer structure comprising at least one first polymer; and ii) at least one at least one polymer and/or polymer derivative, wherein the product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product.
  • a device comprising the product described herein.
  • the device may be an electronic device.
  • the electronic device may be selected from a conductor, a semiconductor, a thin film transistor, an electrode, photocell, circuit, and combinations thereof.
  • an article comprising the product described herein.
  • the article may be wearable.
  • the article may be a textile.
  • the article may be a fibre, jewellery, ceramics, and the like.
  • the product described herein may be used for any one of catalysis, sensing, electrochemical detection, EMI shielding, actuators and energy devices.
  • a formulation for making a polymeric product comprising a composition having at least one first polymerizable component and at least one second polymerizable component.
  • the at least one first polymerizable component is polymerizable to form at least one first polymer structure, wherein at least two phases are formed from the at least one first polymer structure and the at least one second polymerizable component.
  • the product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product.
  • the at least one second polymerizable component is polymerizable to form at least one second polymer.
  • the formulation described herein can be used to control the placement/positioning of components(s) and/or polymer(s) (e.g.
  • the formulation can be used to provide selective positioning of component(s) and/or polymer(s) in a product (e.g. 2D or 3D structure). Therefore, the product may be designed such that specifically selected region(s) have one type of functionality and other region(s) have other type(s) of functionality.
  • a formulation can provide spatially controlled functionality in the product.
  • the selected region(s) and unselected region(s) are near, adjacent, and/or coupled to each other.
  • the first polymer(s) in the selected region(s) and the second polymer(s) in the unselected region(s) are near, adjacent, and/or coupled to each other.
  • the formulation described herein can undergo orthogonal polymerization, different rates of polymerization, and/or have thermodynamic miscibility.
  • each of the polymerization reactions proceed via different mechanisms.
  • a mechanism of a polymerization reaction of the at least one first polymerizable component is different from a mechanism of a polymerization reaction of the at least one second polymerizable component.
  • Other embodiments may include as follows: a sequence of chemical reaction(s) of converting the at least one first polymerizable component (e.g. at least one first monomer and/or at least one first cross-linking agent) to the at least one first polymer, which differs from a sequence of chemical reaction(s) of converting the at least one second polymerizable component (e.g.
  • the chemical reaction(s) may include, for example, radical polymerization (e.g. involves the transfer of a radical from an initiator or building block to another monomer/cross-linking agent), cationic polymerization (e.g. involves the transfer of charge from a cationic initiator or building block to another monomer/cross-linking agent), and thermal polymerization (e.g. involves the addition of two or more molecules to form a larger molecule and eventually a polymer).
  • radical polymerization e.g. involves the transfer of a radical from an initiator or building block to another monomer/cross-linking agent
  • cationic polymerization e.g. involves the transfer of charge from a cationic initiator or building block to another monomer/cross-linking agent
  • thermal polymerization e.g. involves the addition of two or more molecules to form a larger molecule and eventually a polymer.
  • each of the polymerization reactions may proceed via different rates.
  • the rate of polymerizing the at least one first polymerizable component to form at least one first polymer is faster or slower than the rate of polymerizing the at least one second polymerizable component to form at least one second polymer.
  • certain monomer(s) that undergo radical polymerization may form polymers at a faster rate than other monomer(s) that undergo cationic polymerization.
  • (meth)acrylate-based monomers via radical polymerization may form polymers at a faster rate than epoxides via cationic polymerization.
  • Different polymerization rates can also occur within the same mechanism of polymerization (e.g. radical polymerization).
  • acrylates tend to be more reactive in a radical polymerization reaction compared to a radical polymerization reaction with (meth)acrylates.
  • polymerization rates can increase with increasing monomer functionality, for example, from mono- to di- to tri-functional groups.
  • the order of polymerization rates from fastest to slowest is tri-functionalized acrylates>di-functionalized acrylates>mono-functionalized acrylates>(meth)acrylates>epoxides.
  • the at least one first and the at least one second polymerizable components may be selected from monomer(s)/crosslinker(s) of these categories.
  • each of the polymerization reactions may affect the thermodynamic miscibility.
  • thermodynamic miscibility of the at least one first polymer is different from thermodynamic miscibility of the at least one second polymer.
  • the at least one first polymerizable component e.g. a first monomer and/or a first cross-linking agent
  • the molecular weight increases causing the entropy of mixing to be reduced which decreases the miscibility of the at least one second polymerizable component (e.g.
  • phase separation can depend on the solubility and balance of intermolecular forces between each component (each of the first and second monomer(s)/cross-linking agent(s)).
  • Incompatible functional groups in the polymerizable components can affect thermodynamic miscibility, such as polar vs. non-polar, steric vs. non-steric, aliphatic vs. aromatic, aliphatic vs. inorganic, can, for example, influence the solubility and degree of phase separation.
  • the composition has at least one first polymerizable component and at least one second polymerizable component.
  • the composition is a substantially homogeneous composition.
  • the substantially homogeneous composition is a substantially homogeneous mixture.
  • the formulation is capable of achieving polymerization via initiation of polymerization in selected region(s) of the formulation, whereby such polymerization can induce phase separation.
  • polymerization occurs in the selected region(s) to form a first polymer(s) and the unselected region(s) has the second polymerizable component(s). There may be some first polymerizable component(s) in the unselected region(s).
  • the formulation may be contained in, for example, a reservoir prior to polymerization of the selected region(s).
  • the polymerizing may comprise photopolymerization (e.g. photoinduced polymerization).
  • the at least one first polymerizable component has at least one first monomer and/or at least one first cross-linking agent.
  • the at least one second polymerizable component has at least one second monomer and/or at least one second cross-linking agent.
  • the formulation further comprises at least one photoinitiator. Polymerization may also occur via free-radical polymerization without a photoinitiator. With respect to polymerization, the polymerization may be achieved as described above under the many embodiments under the method section.
  • the formulation comprises a first polymerizable component(s) and a second polymerizable component(s).
  • the first polymerizable component(s) comprises monomer(s) and/or crosslinking agent(s), and a photoinitiator(s) in suitable amounts to provide the desired optimal properties.
  • the second polymerizable component(s) comprises thermal curable monomer(s) and/or crosslinking agent(s) in suitable amounts to provide the desired optimal properties.
  • the ratio of first polymerizable and second polymerizable component(s) was varied to optimize the phase separation and physical properties.
  • the formulation of the first polymerizable component(s) and second polymerizable component(s) form a composition (e.g. substantially homogeneous composition or substantially homogeneous mixture).
  • the formulation is capable of being irradiated (e.g. using a desired pattern) to polymerize the first polymerizable component(s), forming a 3D-printed polymer product having spaces or closed regions that confine, mostly, the second polymerizable component(s).
  • the second polymerizable component(s) can be polymerized via thermal or UV curing.
  • phase separation can occur due to orthogonal polymerization mechanisms and/or thermodynamic miscibility of the first polymerizable component(s) and second polymerizable component(s).
  • the final product comprises alternating “hard” and “soft” polymers from the first polymerizable component and the second polymerizable component.
  • the formulation comprises a “hard” polymer resin and a “soft” polymerizable resin.
  • the “hard” polymer resin has (meth)acrylate monomer(s), di(meth)acrylate crosslinker(s), and a photoinitiator(s) in suitable amounts to provide the desired optimal mechanical properties of a “hard” polymer.
  • the “soft” polymer resin has epoxide(s) resin and amine(s) resin in suitable amounts to provide the desired optimal mechanical properties of a “soft” polymer.
  • the ratio of “hard” to “soft” polymer resins was varied to optimize the phase separation and mechanical properties.
  • the formulation of “hard” and “soft” polymer resins form a composition (e.g.
  • the formulation is capable of being irradiated (e.g. using a desired pattern) to polymerize the “hard” polymer resin, forming a “hard” polymer product (e.g. 3D-printed polymer product) having regions that are substantially free of the “hard” polymer (e.g. spaces) but including the “soft” polymer resin.
  • the “hard” polymer product can be heated (e.g. thermally cured) and/or irradiated (e.g. UV cured).
  • the final product comprises both “soft” and “hard” polymers.
  • the formulation comprises a “hard” polymer resin and a “soft” polymerizable resin.
  • the “hard” polymer resin has (meth)acrylate monomer(s), di(meth)acrylate crosslinker(s), and a photoinitiator(s) in suitable amounts to provide the desired optimal mechanical properties of a “hard” polymer.
  • the “soft” polymer resin has epoxide(s) resin and amine(s) resin in suitable amounts to provide the desired optimal mechanical properties of a “soft” polymer.
  • the ratio of “hard” to “soft” polymer resins was varied to optimize the phase separation and mechanical properties.
  • the formulation of “hard” and “soft” polymer resins form a composition (e.g.
  • the formulation is capable of being irradiated (e.g. using a desired pattern) to polymerize the “hard” polymer resin, forming a “hard” polymer product (e.g. 3D-printed polymer product) having closed regions that are substantially free of the “hard” polymer (e.g. spaces) but trap the “soft” polymer resin (e.g. resin filled closed regions).
  • the “hard” polymer product having the confined “soft” polymer resin can be heated (e.g. thermally cured) and/or irradiated (e.g. UV cured).
  • the final product comprises both “soft” and “hard” polymers.
  • the formulation comprises a first polymerizable component(s) and a second polymerizable component(s).
  • the first polymerizable component(s) comprise monomer(s) and/or cross-linking agent(s), and a photoinitiator(s) in suitable amounts to provide the desired optimal properties.
  • the second polymerizable component(s) comprises monomer(s) and/or crosslinker(s), and photoinitiator(s) in suitable amounts to provide the desired optimal properties.
  • the ratio of the first polymerizable and second polymerizable components was varied to optimize the phase separation and physical properties.
  • the formulation of first polymerizable component(s) and second polymerizable component(s) form a composition (e.g.
  • the formulation is capable of being irradiated (e.g. using a desired pattern) to polymerize the first polymerizable component polymer resin, forming a 3D-printed polymer product having closed regions that confine, mostly, the second polymerizable component(s).
  • the second polymerizable component are polymerizable via thermal or UV curing.
  • phase separation occurs due to orthogonal polymerization mechanisms, different rates of polymerization, and/or thermodynamic miscibility of the first polymerizable component(s) and second polymerizable component(s).
  • the final product comprises alternating “hard” and “soft” polymers from the first polymerizable component(s) and the second polymerizable component(s).
  • the formulation comprises a “soft” polymer resin and a “hard” polymerizable resin.
  • the “soft” polymer resin has (meth)acrylate monomer(s), di(meth)acrylate crosslinker(s), and a photoinitiator(s) in suitable amounts to provide the desired optimal mechanical properties of a “soft” polymer.
  • the “hard” polymer resin has epoxide(s) resin and amine(s) resin in suitable amounts to provide the desired optimal mechanical properties of a “hard” polymer.
  • the ratio of “soft” to “hard” polymer resins was varied to optimize the phase separation and mechanical properties.
  • the formulation of “soft” and “hard” polymer resins form a composition (e.g.
  • the formulation is capable of being irradiated (e.g. using a desired pattern) to polymerize the “soft” polymer resin, forming a “soft” polymer product (e.g. 3D-printed polymer product) having closed regions that confine mostly “hard” polymer resin and some “soft” polymer resin (e.g. resin filled closed regions).
  • the “soft” polymer product having the confined “hard” polymer resin and some “soft” polymer resin is capable of being heated (e.g. thermally cured) and/or irradiated (e.g. UV cured).
  • the final product comprises both “soft” and “hard” polymers.
  • the formulation comprises a “hard” polymer resin and a “soft” polymerizable resin.
  • the “hard” polymer resin has (meth)acrylate monomer(s), and di(meth)acrylate crosslinker(s), one or both of which contains an epoxide functional group, and a photoinitiator(s) in suitable amounts to provide the desired optimal mechanical properties of a “hard” polymer.
  • the “soft” polymer resin has epoxide(s) resin (e.g. UV curable) or amine(s) resin (thermal curable) and a cationic initiator in suitable amounts to provide the desired optimal mechanical properties of a “soft” polymer.
  • the ratio of “hard” to “soft” polymer resins was varied to optimize the phase separation and mechanical properties.
  • the formulation of “hard” and “soft” polymer resins form a composition (e.g. substantially homogeneous composition or substantially homogeneous mixture).
  • the formulation is capable of being irradiated (e.g. using a desired pattern) to polymerize the “hard” polymer resin, forming a “hard” polymer product (e.g. 3D-printed polymer product) having regions that include the “soft” polymer resin (e.g. filled regions).
  • the “hard” polymer product having the “soft” polymer resin is capable of being heated (e.g. thermally cured) and/or irradiated (e.g.
  • the formulation has first polymer(s) that may have at least one functional group that can react with the second polymerizable component(s), which polymerizes the second polymerizable component(s) to the second polymer(s), and/or reacts with the second polymer(s).
  • the first polymer(s) are capable of bonding/tethering to the second polymer(s) and/or the second polymerizable component(s).
  • the formulation comprises at least one first polymerizable component and at least one second polymerizable component to form a composition.
  • the at least one first polymerizable component is polymerizable to form at least one first polymer, wherein at least two phases are formed from the at least one first polymer and the at least one second polymerizable component.
  • the at least one second polymerizable component is polymerizable to form at least one second polymer, and wherein the product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product.
  • the first polymer(s) may have at least one functional group that are capable of reacting with the second polymerizable component(s), which polymerizes the second polymerizable component(s) to the second polymer(s), and/or reacts with the second polymer(s).
  • the first polymer(s) are bonded/tethered to the second polymer(s) and/or the second polymerizable component(s).
  • the formulation comprises a “hard” polymer resin, a “soft” polymerizable resin and a photoinitiator.
  • the “hard” polymer resin has (meth)acrylate monomer(s), and di(meth)acrylate crosslinker(s) in suitable amounts to provide the desired optimal mechanical properties of a “hard” polymer.
  • the “soft” polymer resin has (meth)acrylate monomer(s), and di(meth)acrylate crosslinker(s), with slower kinetics and/or incompatible functional groups, in suitable amounts to provide the desired optimal mechanical properties of a “soft” polymer.
  • the ratio of “hard” to “soft” polymer resins was varied to optimize the phase separation and mechanical properties.
  • the formulation of “hard” and “soft” polymer resins form a composition (e.g. substantially homogeneous composition or substantially homogeneous mixture).
  • the formulation is capable of being irradiated (e.g. using a desired pattern) to polymerize the “hard” polymer resin, forming a “hard” polymer product (e.g. 3D-printed polymer product) having regions, whereby the “soft” polymer resin separates and diffuses to the regions in the “hard” polymer product.
  • Phase separation of the “soft” polymer resin into the regions in the “hard” polymer product may occur due to kinetics (e.g. slower photopolymerization) and/or incompatible groups (e.g. acrylates and methacrylates that are polar vs.
  • the “hard” polymer product having the “soft” polymer resin is capable of being heated (e.g. thermally cured) and/or irradiated (e.g. UV cured) to polymerize the “soft” resin.
  • the final product comprises both “soft” and “hard” polymers.
  • the formulation comprises a “hard” polymer resin, a “soft” polymerizable resin, a photoinitiator, a cationic photoinitiator, and a photosensitizer.
  • the “hard” polymer resin has (meth)acrylate monomer(s), and di(meth)acrylate crosslinker(s) in suitable amounts to provide the desired optimal mechanical properties of a “hard” polymer.
  • the “soft” polymer resin has epoxide monomer(s) and epoxide crosslinking agent(s) in suitable amounts to provide the desired optimal mechanical properties of a “soft” polymer.
  • the ratio of “hard” to “soft” polymer resins was varied to optimize the phase separation and mechanical properties.
  • the formulation of “hard” and “soft” polymer resins form a composition (e.g. substantially homogeneous composition or substantially homogeneous mixture).
  • the formulation is capable of being irradiated (e.g. using a desired pattern) to polymerize the “hard” polymer resin, forming a “hard” polymer product (e.g. 3D-printed polymer product) having regions, whereby the “soft” polymer resin separates and diffuses to the regions in the “hard” polymer product.
  • Phase separation of the “soft” polymer resin into the regions in the “hard” polymer product may occur due to kinetics (e.g. slower photopolymerization) and/or incompatible groups (e.g. acrylates and methacrylates that are polar vs.
  • the “hard” polymer product having the “soft” polymer resin is capable of being heated (e.g. thermally cured) and/or irradiated (e.g. UV cured) to polymerize the “soft” resin.
  • the final product comprises both “soft” and “hard” polymers.
  • the phase separation and architecture of the final 3D printed product may be defined by the kinetics, mechanisms of polymerization, and/or thermodynamic miscibility of the components and the patterned illumination of the 3D structure.
  • the resulting unique structural motifs can create an overall product with different or improved physical/chemical properties. For example, alternating “hard” and “soft” phases (e.g. “hard” and “soft” polymers) improves the overall mechanical properties compared to similar structures of only the individual polymer.
  • phase separated functional materials e.g. first polymer(s) and second polymer(s) allow certain regions to be conductive, responsive to external stimuli, etc.
  • the first polymer(s) e.g. formed from the first monomer(s) and/or the first cross-linking agent(s)
  • the second polymer(s) e.g. formed from the second monomer(s) and/or the second cross-linking agent(s)
  • the first polymer(s) formed from polymerizing the first polymerizable component(s) may have mechanical properties that are characterized as “hard” or “soft”, while the second polymer(s) formed from polymerizing the slower, orthogonal and/or lower soluble second polymerizable component(s) may have mechanical properties that are characterized to be the opposite of the first polymer(s); “soft” or “hard”.
  • a “hard” polymer may have the following mechanical properties: about 2000 to about 4000 MPa range in modulus of elasticity, about 40 to about 65 MPa range in tensile strength, and/or about 10 to about 25% range in elongation at break;
  • a “soft” polymer may have the following mechanical properties: about 0.5 to about 5.0 MPa range in tensile strength and/or about 45 to about 250% range in elongation at break.
  • first polymer(s) and the second polymer(s) may be nanomaterials, dyes/pigments, conductive, tolerant, piezoelectric, responsive to external stimuli, and/or different environmental conditions, etc.
  • External stimuli or environmental conditions can include temperature, pressure, surrounding environment (water or other chemicals), magnetic field, etc.
  • the formulation comprises a composition having at least one first polymerizable component and at least one polymer and/or polymer derivative thereof.
  • the at least one first polymerizable component is polymerizable to form at least one first polymer structure, wherein at least two phases are formed from the at least one first polymer structure and the at least one polymer and/or polymer derivative thereof.
  • the product is a functional product, a functional precursor product, or a combination of a functional and functional precursor product.
  • the formulation comprises a composition having at least one first polymerizable component and a polymer and/or polymer derivative thereof.
  • the at least one first polymerizable component is polymerizable to form a 3D printed first polymer structure, wherein two phases are formed from the 3D printed first polymer structure and the at least one polymer and/or polymer derivative thereof.
  • the first polymerizable component comprises monomer(s) and/or crosslinking agent(s), and a photoinitiator(s) in suitable amounts to provide the desired optimal mechanical properties.
  • the at least one polymer and/or polymer derivative thereof is capable of phase separating due to thermodynamic miscibility of the first polymerizable component and the at least one polymer and/or polymer derivative thereof.
  • the ratio of first polymerizable component(s) and the at least one polymer and/or polymer derivative thereof may be varied to optimize the phase separation and desired resulting properties.
  • the first polymerizable component(s) and the at least one polymer and/or polymer derivative thereof were combined to form a composition (e.g. substantially homogeneous composition or substantially homogeneous mixture).
  • the mixture was irradiated (e.g. using a desired pattern) to polymerize the first polymerizable component, forming a 3D-printed polymer structure in which the at least one polymer and/or polymer derivative thereof is either confined within the structure and phase separated out of the spaces or phase separated out of the 3D structure and into the spaces.
  • any suitable amount can be used.
  • One embodiment includes from about 10% to about 99% by weight based on the weight of the homogeneous mixture. In some embodiments, the amount is from about 20% to about 99% by weight, from about 30% to about 99% by weight, from about 40% to about 99% by weight, from about 50% to about 99% by weight, from about 60% to about 99% by weight, from about 70% to about 99% by weight, or from about 80% to about 99% by weight based on the weight of the homogeneous mixture.
  • the product may be any suitable structure/object.
  • the product may be a 3D- or 2D-product.
  • the product is a film or a 3D-product.
  • the product may have any desired geometry (e.g. shape).
  • Various 3D structures and functional high aspect ratio coatings and functional patterns in devices such as sensors, optoelectronic devices, solar cells, electrodes, RFID tags, antennas, electroluminescent devices, power sources and connectors for circuit boards may be fabricated.
  • the product may have at least one functional property selected from the group consisting of chemical properties, mechanical properties, magnetic properties, optical properties, insulating or protective properties (e.g. towards heat, radiation, mechanical abrasion), properties, electrical properties, electrochemical, catalytic properties, and combinations thereof.
  • the product is at least one of stretchable, flexible, lightweight, porous, conductive, non-conductive, surface durable, increased surface area, hydrophobic, biocompatible, anti-bacterial, mould resistant, wear-resistant, heat resistant, cold resistant, improved surface properties (antifouling), reduce flame retardancy, and combinations thereof.
  • the surface of the functional product e.g. coating itself, coating of 3D-product, etc.
  • the product is multifunctional and/or is a precursor product that is a precursor to a multifunctional product. The product may be used for various applications, including metal/semiconductor, catalysis, sensing, electrochemical detection, EMI shielding, actuators and energy devices.
  • inventions of commercial uses for the product include, for example, metamaterials with millimetre wave communication devices, objects embedded with self-healing materials, 3D objects with responsive materials (ferrofluidics, piezoelectric materials, conductive channels, etc.) for soft robotics, shape recovery objects with controlled placement/positioning of actuation material, encryption or anti-counterfeiting with treatment of spatially controlled structures with fluorescent ink, and/or parts for structural electronics (sensors and energy devices) with spatially controlled placement/positioning of conductive material within an object.
  • the product is conductive.
  • the product may be selected to be any suitable conductivity.
  • it may have a conductivity (e.g. resistance) of at least about 1 ⁇ /cm; at least about 2 ⁇ /cm; at least about 5 ⁇ /cm; at least about 10 ⁇ /cm; at least about 15 ⁇ /cm; or at least about 20 ⁇ /cm.
  • the conductivity may be from about 1 to about 50 ⁇ /cm; from about 2 to about 50 ⁇ /cm; from about 5 to about 50 ⁇ /cm; from about 10 to about 50 ⁇ /cm; from about 15 to about 50 ⁇ /cm; from about 20 to about 50 ⁇ /cm; from about 1 to about 40 ⁇ /cm; from about 2 to about 40 ⁇ /cm; from about 5 to about 40 ⁇ /cm; from about 10 to about 40 ⁇ /cm; from about 15 to about 40 ⁇ /cm; from about 20 to about 40 ⁇ /cm; from about 1 to about 30 ⁇ /cm; from about 2 to about 30 ⁇ /cm; from about 5 to about 30 ⁇ /cm; from about 10 to about 30 ⁇ /cm; from about 15 to about 30 ⁇ /cm; from about 20 to about 30 ⁇ /cm; from about 1 to about 25 ⁇ /cm; from about 2 to about 25 ⁇ /cm; from about 5 to about 25
  • the formulation described herein can further comprise at least one first component.
  • the first component(s) comprises at least one functional component, at least one functional precursor component, or a combination thereof.
  • the at least one functional precursor component is capable of being converted into at least one second functional component.
  • the at least one second functional component is different from said at least one functional component.
  • the at least one second functional component is the same as the at least one functional component.
  • the converting may comprise sintering and/or pyrolyzing, for example, as described above.
  • the at least one functional precursor component is capable of being converted into at least one second functional component via sintering.
  • the sintering may be at least one of thermal sintering, UV-VIS radiation sintering, and laser sintering. In embodiments, sintering may occur during or after printing.
  • the formulation is capable of being sintered to form the product, pyrolyzed to form the product, or sintered and pyrolyzed to form the product.
  • sintering is thermal sintering, UV-VIS radiation sintering, laser sintering or any combination thereof.
  • minimum thermal sintering temperatures are selected based on a minimum temperature for converting the functional precursor to the functional product.
  • Maximum thermal sintering temperatures may be selected based on a maximum temperature that the functional precursor and/or the functional product may be heated to without causing substantive decomposition or degradation. With respect to thermal sintering, the temperature ranges include, but are not limited thereto, from about 50° C.
  • Thermal sintering may occur under air or under inert condition(s), such as nitrogen. Thermal sintering may be performed for a time in ranges of about 15 minutes to about 180 minutes, or about 30 minutes to about 120 minutes, or about 45 minutes to about 60 minutes. In typical embodiments, sintering occurs under nitrogen with about 500 ppm oxygen.
  • sintering energies may range from about 1 J/cm 2 to about 30 J/cm 2 , or about 2 J/cm 2 to about 10 J/cm 2 , or about 2.5 J/cm 2 to about 5 J/cm 2 , or about 2.4 J/cm 2 to about 3.1 J/cm 2 .
  • the pulse widths are about 500 s to about 5000 s, or about 1000 s to about 4000 s, or about 2500 s to about 3000 s.
  • UV-VIS radiation sintering occurs under air.
  • the temperature ranges include, but are not limited thereto, from about 350° C.
  • Pyrolyzing may be performed for a time in a range of about 1 to about 60 minutes. Pyrolyzing may occur under air or under inert condition(s), such as nitrogen.
  • the first and second polymer(s) have a weight average molecular weight of about 10,000 to about 10,000,000, or about 10,000 to about 5,000 000, or about 10,000 to about 1,000,000, or about 50,000 to about 1,000,000, or about 50,000 to about 500,000. It is understood that the weight average molecular weight may approach infinity and includes cross-linked polymeric network(s).
  • each, independently, may comprise at least one monomer and/or at least one oligomer.
  • the at least one first and second polymerizable component(s) may comprise at least one liquid monomer and/or at least one liquid oligomer.
  • the at least one first polymerizable component and/or the at least one second polymerizable component comprises at least one resin.
  • Some examples include resins based on epoxies, vinyl ethers, acrylates, urethane-acrylates, methacrylates, acrylamides, thiol-ene based resins, styrene, siloxanes, silicones, and any functionalized derivatives thereof (e.g.
  • the at least one resin may comprise at least one commercial resin.
  • typical examples of the at least one resin comprises at least one commercial resin for 3D printing such as, and without being limited thereto, 3D printing via photoactivation (e.g. stereolithographic (SLA) printing or digital light processing (DLP)).
  • the at least one resin may comprise at least one acrylate based-resin.
  • the monomer resins may be elastomers or pre-ceramic polymers.
  • the monomers and oligomers are selected according to their physico-chemical and chemical properties, such as monomer viscosity and/or surface tension, and/or polymer elasticity and/or hardness, number of polymerizable groups, and according to the printing method and the polymerization reaction type, e.g., the radiation source or heat source of choice.
  • modulus value ranges of from about 0.1 MPa to about 8000 MPa.
  • the monomers are selected from acid containing monomers, acrylic monomers, amine containing monomers, cross-linking acrylic monomers, dual reactive acrylic monomers, epoxides/anhydrides/imides, fluorescent acrylic monomers, fluorinated acrylic monomers, high or low refractive index monomers, hydroxy containing monomers, mono and difunctional glycol oligomeric monomers, styrenic monomers, vinyl and ethenyl monomers.
  • the monomers can polymerize to yield conductive polymers such as polypyrole and polyaniline.
  • the at least one monomer is selected from dipentaerythnitol hexaacrylate (DPHA) and trimethylolpropane triacrylate (TMPTA).
  • the at least one oligomer is selected from the group consisting of acrylates and vinyl containing molecules.
  • the monomer can be any monomeric compound having a functional group, such as an activatable photopolymerizable group (photoinduced polymerization) that can propagate, for example, carbon-carbon, carbon-oxygen, carbon-nitrogen, or carbon-sulfur bond formation.
  • the monomer is selected from mono-functional monomers (e.g. monomers with one functional group). During polymerization, the radical of the monofunctional monomer is formed and it will react with other monomers present to form oligomers and polymers. The resultant oligomers and polymers can have different properties depending on its structure. Some monomers may be selected depending on their flexibility, viscosity, curing rate, reactivity or toxicity.
  • the monomer is polymerized to form a polyacrylate such as polymethylmethacrylate, an unsaturated polyester, a saturated polyester, a polyolefin (polyethylenes, polypropylenes, polybutylenes, and the like), an alkyl resin, an epoxy polymer, a polyamide, a polyimide, a polyetherimide, a polyamideimide, a polyesterimide, a polyesteramideimide, polyurethanes, polycarbonates, polystyrenes, polyphenols, polyvinylesters, polysilicones, polyacetals, cellulose acetates, polyvinylchlorides, polyvinylacetates, polyvinyl alcohols polysulfones, polyphenylsulfones, polyethersulfones, polyketones, polyetherketones, poyletheretherketones, polybenzimidazoles, polybenzoxazoles, polybenzthiazoles, polyfluorocarbones,
  • polyacrylates include polyisobomylacrylate, polyisobornylmethacrylate, polyethoxyethoxyethyl acrylate, poly-2-carboxyethylacrylate, polyethylhexylacrylate, poly-2-hydroxyethylacrylate, poly-2-phenoxylethylacrylate, poly-2-phenoxyethylmethacrylate, poly-2-ethylbutylmethacrylate, poly-9-anthracenylmethyl methacrylate, poly-4-chlorophenylacrylate, polycyclohexylacrylate, polydicyclopentenyloxyethyl acrylate, poly-2-(N,N-diethylamino)ethyl methacrylate, poly-dimethylaminoeopentyl acrylate, poly-caprolactone 2-(methacryloxy)ethylester, and polyfurfurylmethacrylate, poly(ethylene glycol)meth
  • Monomers that may be used include acrylic monomers such as monoacrylics, diacrylics, triacrylics, tetraacrylics, pentacrylics, etc.
  • examples of other monomers include ethyleneglycol methyl ether acrylate, N,N-diisobutyl-acrylamide, N-vinyl-pyrrolidone, (meth)acryloyl morpholine, 7-amino-3,7-dimethyloctyl, (meth) acrylate, isobutoxymethyl (meth) acrylamide, isobornyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl (meth)acrylate, ethyldiethylene glycol (meth)acrylate, t-octyl (meth)acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl
  • epoxide monomers such as 3,4-epoxyclyclohexylmethyl 3,4-epoxycylcohexanecarboxylate, epoxycyclohexylethyl terminated polydimethylsiloxane, bisphenol A diglycidyl ether, allyl glycidyl ether, bis[4-(glycidyloxy)phenyl]methane, 1,3-butadiene diepoxide, 1,4-butanediol diglycidyl ether, butyl glycidyl ether, tert-butyl glycidyl ether, 4-chlorophenyl glycidyl ether, cyclohexene oxide, dicyclopentadiene dioxide, 1,2,7,8-diepoxycyclooctane, 1,2,5,6-diepoxyoctane, styrene oxide, neopent
  • epoxide monomers such as
  • any suitable amount can be used depending on the desired functional and/or functional precursor product.
  • One embodiment includes from about 10% to about 99% by weight of the at least one monomer based on the weight of the composition.
  • the amount is from about 15% to about 90% by weight, from about 15% to about 85% by weight, from about 15% to about 80% by weight, from about 15% to about 75% by weight, from about 20% to about 90% by weight, from about 30% to about 90% by weight, from about 35% to about 90% by weight, from about 45% to about 90% by weight, from about 50% to about 90% by weight, from about 55% to about 90% by weight, from about 60% to about 90% by weight, from about 30% to about 80% by weight, from about 35% to about 80% by weight, from about 40% to about 80% by weight, from about 45% to about 80% by weight, or from about 50% to about 80% by weight based on the weight of the composition.
  • the amount of the at least one monomer that may be used in embodiments based on the weight of the at least one polymerizable component itself includes from about 1% to about 90% by weight of the at least one monomer. In some embodiments, the amount is from about 1% to about 85% by weight, from about 1% to about 80% by weight, from about 1% to about 75% by weight, from about 5% to about 90% by weight, from about 10% to about 90% by weight, from about 15% to about 90% by weight, from about 20% to about 90% by weight, from about 25% to about 90% by weight, from about 35% to about 90% by weight, from about 40% to about 90% by weight, from about 45% to about 90% by weight, from about 5% to about 80% by weight, from about 10% to about 80% by weight, from about 15% to about 80% by weight, from about 20% to about 80% by weight, or from about 50% to about 80% by weight based on the weight of the at least one polymerizable component.
  • Cross-linking agents may have one or more functional groups and, typically, have two or more functional groups (e.g. di-, tri-, tetra-, etc. functional cross-linking agents).
  • the functional groups may be present at both ends of the cross-linking agent, forming branched polymerization, whereby the cross-linking agent may react with two or more polymers.
  • a 2D product is formed with a monofunctional cross-linking agent and a 3D product is formed with a multifunctional cross-linking agent.
  • the morphology of a functional and/or functional precursor product may depend on the concentration (e.g. amount) of cross-linking agent.
  • concentration of the cross-linking agent may control the rate at which a polymer network forms.
  • the rate at which the monomers form polymer networks e.g. branched polymerization
  • High rates of polymer network formation may limit the diffusion of slower reacting or non-polymerizing components and provide more uniform compositions such as composites in certain regions (e.g. portions) of the product.
  • the morphology of the functional and/or functional precursor product can be a function of cross-linking agent concentrations in compositions (e.g. substantially homogeneous composition or substantially homogeneous mixture) containing non-polymerizing functional and/or functional precursor components.
  • the amount of functional and/or functional precursor component at the surface of the functional and/or functional precursor product decreases with increased concentration of cross-linking agent.
  • the concentration of functional and/or functional precursor component at the surface can determine the resistance value of the printed product.
  • the resistance of the functional and/or functional precursor component at the surface increases in view of the lower concentration of the functional and/or functional precursor component at the surface.
  • any suitable amount can be used depending on the desired functional and/or functional precursor product.
  • the amount of the at least one cross-linking agent can be used to tune the morphology of the functional and/or functional precursor product.
  • One embodiment includes from about 10% to about 99% mol based on the composition.
  • the amount is from about 80% to about 99% mol, from about 85% to about 99% mol, from about 90% to about 99% mol, from about 10% to about 80% mol, from about 10% to about 70% mol, from about 10% to about 60% mol, from about 10% to about 50% mol, from about 10% to about 40% mol, from about 10% to about 35% mol, from about 20% to about 80% mol, from about 25% to about 80% mol, from about 30% to about 80% mol, from about 35% to about 80% mol, from about 40% to about 80% mol, from about 45% to about 80% mol, from about 50% to about 80% mol, from about 55% to about 80% mol, from about 60% to about 80% mol, from about 65% to about 80% mol, from about 70% to about 80% mol, from about 35% to about 75% mol, from about 35% to about 70% mol, from about 35% to about 65% mol, from about 35% to about 60% mol, from about 3
  • any suitable amount can be used.
  • One embodiment includes from about 10% to about 99% by weight of the at least one cross-linking agent based on the weight of the homogeneous mixture.
  • the amount is from about 15% to about 90% by weight, from about 15% to about 85% by weight, from about 15% to about 80% by weight, from about 15% to about 75% by weight, from about 20% to about 90% by weight, from about 30% to about 90% by weight, from about 35% to about 90% by weight, from about 45% to about 90% by weight, from about 50% to about 90% by weight, from about 55% to about 90% by weight, from about 60% to about 90% by weight, from about 30% to about 80% by weight, from about 35% to about 80% by weight, from about 40% to about 80% by weight, from about 45% to about 80% by weight, or from about 50% to about 80% by weight based on the weight of the composition.
  • the amount of the at least one cross-linking agent that may be used in embodiments based on the weight of the at least one polymerizable component itself includes from about 10% to about 99% by weight of the at least one cross-linking agent.
  • the amount is from about 15% to about 90% by weight, from about 15% to about 85% by weight, from about 15% to about 80% by weight, from about 15% to about 75% by weight, from about 20% to about 90% by weight, from about 30% to about 90% by weight, from about 35% to about 90% by weight, from about 45% to about 90% by weight, from about 50% to about 90% by weight, from about 55% to about 90% by weight, from about 60% to about 90% by weight, from about 30% to about 80% by weight, from about 35% to about 80% by weight, from about 40% to about 80% by weight, from about 45% to about 80% by weight, or from about 50% to about 80% by weight based on the weight of the at least one polymerizable component (e.g. resin).
  • portions of the functional and/or functional precursor product are a composite.
  • the amount of the at least one crosslinking agent used to make the product is from about 80% to about 99% mol, from about 85% to about 99% mol, or from about 90% to about 99% mol based on the mol of the homogeneous mixture.
  • the at least one cross-linking agent comprises at least one difunctional cross-linking agent.
  • the at least one cross-linking agent comprises at least one trifunctional cross-linking agent.
  • the at least one cross-linking agent comprises at least one tetrafunctional cross-linking agent.
  • the at least one cross-linking agent comprises at least one difunctional cross-linking agent.
  • portions of the functional and/or functional precursor product is graded and/or coated.
  • the amount of the at least one crosslinking agent used to make the product is from about 10% to about 80% mol, from about 10% to about 70% mol, from about 10% to about 60% mol, from about 10% to about 50% mol, from about 10% to about 40% mol, from about 10% to about 35% mol, from about 20% to about 80% mol, from about 25% to about 80% mol, from about 30% to about 80% mol, from about 35% to about 80% mol, from about 40% to about 80% mol, from about 45% to about 80% mol, from about 50% to about 80% mol, from about 55% to about 80% mol, from about 60% to about 80% mol, from about 65% to about 80% mol, from about 70% to about 80% mol, from about 35% to about 75% mol, from about 35% to about 70% mol, from about 35% to about 65% mol, from about 35% to about 60% mol, from about 3
  • the at least one cross-linking agent comprises at least one difunctional cross-linking agent. In other embodiments, the at least one cross-linking agent comprises at least one trifunctional cross-linking agent. In other embodiments, the at least one cross-linking agent comprises at least one tetrafunctional cross-linking agent. In a typical embodiment, the at least one cross-linking agent comprises at least one difunctional cross-linking agent.
  • portions of the functional and/or functional precursor product are graded.
  • the amount of the at least one crosslinking agent used to make the product is from about 10% to about 80% mol, from about 10% to about 70% mol, from about 10% to about 60% mol, from about 10% to about 50% mol, from about 10% to about 40% mol, from about 10% to about 35% mol, from about 20% to about 80% mol, from about 25% to about 80% mol, from about 30% to about 80% mol, from about 35% to about 80% mol, from about 40% to about 80% mol, from about 45% to about 80% mol, from about 50% to about 80% mol, from about 55% to about 80% mol, from about 60% to about 80% mol, from about 65% to about 80% mol, from about 70% to about 80% mol, from about 35% to about 75% mol, from about 35% to about 70% mol, from about 35% to about 65% mol, from about 35% to about 60% mol, from about 35% to about 5
  • the at least one cross-linking agent comprises at least one difunctional cross-linking agent. In other embodiments, the at least one cross-linking agent comprises at least one trifunctional cross-linking agent. In other embodiments, the at least one cross-linking agent comprises at least one tetrafunctional cross-linking agent.
  • portions of the functional and/or functional precursor product are coated.
  • the amount of the at least one crosslinking agent used to make the product is from about 15% to about 50% mol, from about 15% to about 45% mol, from about 15% to about 40% mol, or from about 15% to about 35% mol based on the mol of the homogeneous mixture.
  • the at least one cross-linking agent comprises at least one difunctional cross-linking agent.
  • the at least one cross-linking agent comprises at least one trifunctional cross-linking agent.
  • the at least one cross-linking agent comprises at least one tetrafunctional cross-linking agent.
  • the at least one cross-linking agent comprises at least one difunctional cross-linking agent.
  • any suitable amount can be used.
  • One embodiment includes from about 10% to about 99% by weight of the at least one cross-linking agent based on the weight of the homogeneous mixture.
  • the amount is from about 15% to about 90% by weight, from about 15% to about 85% by weight, from about 15% to about 80% by weight, from about 15% to about 75% by weight, from about 20% to about 90% by weight, from about 30% to about 90% by weight, from about 35% to about 90% by weight, from about 45% to about 90% by weight, from about 50% to about 90% by weight, from about 55% to about 90% by weight, from about 60% to about 90% by weight, from about 30% to about 80% by weight, from about 35% to about 80% by weight, from about 40% to about 80% by weight, from about 45% to about 80% by weight, or from about 50% to about 80% by weight based on the weight of the homogeneous mixture.
  • the amount of the at least one cross-linking agent that may be used in embodiments based on the weight of the at least one polymerizable component itself includes from about 10% to about 99% by weight of the at least one cross-linking agent.
  • the amount is from about 15% to about 90% by weight, from about 15% to about 85% by weight, from about 15% to about 80% by weight, from about 15% to about 75% by weight, from about 20% to about 90% by weight, from about 30% to about 90% by weight, from about 35% to about 90% by weight, from about 45% to about 90% by weight, from about 50% to about 90% by weight, from about 55% to about 90% by weight, from about 60% to about 90% by weight, from about 30% to about 80% by weight, from about 35% to about 80% by weight, from about 40% to about 80% by weight, from about 45% to about 80% by weight, or from about 50% to about 80% by weight based on the weight of the at least one polymerizable component (e.g. resin).
  • the cross-linking agent is a radical reactive cross-linking agent.
  • the radical reactive cross-linking agent include a methacrylic compound, an acrylic compound, a vinyl compound, and an allyl compound.
  • suitable cross-linking agents which can be used to form polyacrylates include 2,2-bis(4-methacryloxyphenyl)propane, 1,2-butanediol diacrylate, 1,4-butanediol diacrylate, ethylene glycol diacrylate, di(ethylene glycol) diacrylate, tetra(ethylene glycol) diacrylate, ethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,4-cyclohexanediol dimethacrylate, 1,10-decanediol dimethacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, dimethylpropanediol dimethacrylate, triethylene glycol dimethacrylate,
  • triacrylates which can be used to form polyacrylates include tris(2-hydroxyethyl)isocyanurate trimethacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate and pentaerythritol triacrylate.
  • tetracrylates include pentaerythritol tetraacrylate, di(trimethylolpropane) tetraacrylate, and ethoxylated pentaerythritol tetraacrylate.
  • pentaacrylates include dipentaerythritol pentaacrylate and pentaacrylate ester.
  • cross-linking agents include: ethylene glycol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, triethylene glycol diacrylate, tetraethylene glycoldi(meth)acrylate, tricyclodecanediyl-dimethylene di(meth)acrylate, tris(2-hydroxyethyl) isocyanurate di(meth)acrylate, tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, caprolactone modified tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, trimethylolpropane tri(meth) acrylate, EO modified trimethylolpropane tri(meth)acrylate, PO modified trimethylolpropane tri(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, both terminal (meth)acrylic acid adduct of bisphenol A
  • the radiation source employed for initiating the polymerization is selected based on the type of photoinitiator used.
  • the photoinitiator is a chemical compound that decomposes into free radicals when exposed to light but cationic photoinitiators may be used as well.
  • photoinitiators There are a number of photoinitiators known in the art.
  • suitable photoinitiators include, but are not limited to, ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate, 7-diethylamino-2-coumarin, acetophenone, p-tert-butyltrichloro acetophenone, chloro acetophenone, 2-2-diethoxy acetophenone, hydroxy acetophenone, 2,2-dimethoxy-2′-phenyl acetophenone, 2-amino acetophenone, dialkylamino acetophenone, benzil, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-2-methylpropane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane
  • One embodiment includes less than about 0.5% by weight of the at least one photoinitiator based on the weight of the homogeneous mixture. In some embodiments, the amount is less than about 0.4% by weight, less than about 0.3% by weight, or less than about 0.1% by weight based on the weight of the homogeneous mixture.
  • the amount of the at least one photoinitiator that may be used in embodiments based on the weight of the at least one polymerizable component itself includes less than about 3% by weight of the at least one photoinitiator. In some embodiments, the amount is less than about 3% by weight, less than about 1.8% by weight, less than about 1.5% by weight, or less than about 1% by weight based on the weight of based on the weight of the at least one polymerizable component (e.g. resin).
  • the photosensitizers are used to initiate polymerization (e.g. may initiate formation of free radicals from a photoinitiator).
  • a photoinitiator e.g. may initiate formation of free radicals from a photoinitiator.
  • photosensitizers known in the art. A skilled person would understand a suitable amount of photosensitizers that may be used to initiate a photopolymerization reaction.
  • suitable photosensitizers include, but are not limited to, isopropyl-9H-thioxanthen-9-one, anthracene, phenothiazine, perylene, thioxanthone, benzophenone, acetophenone, pyrene, acridinedione, boron-dipyrromethenes, curcumin, coumarin, etc.
  • the ratios of the components of the at least one polymerizable component any suitable ratios can be used depending on the desired functional and/or functional precursor product.
  • the ratio of the at least one monomer to at least one cross-linking agent includes about 9:1 to about 0:10 based on % by weight.
  • the amount is about 9:1 to about 1:9 based on % by weight, about 8:2 to about 2:8 based on % by weight, about 7:3 to about 3:7 based on % by weight, about 6:4 to about 4:6 based on % by weight, about 5:5 to about 5:5 based on % by weight, about 4:6 to about 6:4 based on % by weight, about 3:7 to about 7:3 based on % by weight, about 2:8 to about 8:2 based on % by weight, or about 1:10 to about 9:1 based on % by weight.
  • the ratio of the at least one monomer to at least one cross-linking agent to at least one photoinitiator includes about 8.9:1:0.1 to about 0:9.9:0.1 based on % by weight.
  • the attractive and repulsive forces (hydrophobic/hydrophilic interactions) between components may be leveraged to control the placement of functional components.
  • the components When components have similar hydrophilic or hydrophobic properties, the components will have less of a driving force to phase separate upon polymerization. If the components differ in their hydrophobicity or hydrophilicity, the functional component will have a larger driving force to separate from the composition (e.g. substantially homogenous polymerizing monomer/cross-linking agent composition/mixture).
  • the resulting product may be used as a scaffold for receiving metallic functional components (e.g. through electroplating) and as barrier type coatings (e.g. hydrophobic), dielectrics or insulating material, and may be selected for the desired flexibility and strength needed in the final product.
  • the at least one first component can separate and migrate towards a region where the concentration of the at least one first polymerizable component is greater (which may be slowly decreasing with polymerization) and the at least one second polymerizable component is greater and forms a composite coating of, mostly, the first component and the at least one second polymerizable component.
  • the at least one first component can separate and migrate towards a region where the concentration of the at least one second polymerizable component is greater and forms a coating of the first component.
  • the product comprises at least about 0.1% by weight of the at least one first component, or at least about 1% by weight of the at least one first component, or at least about 3% by weight of the at least one first component, or at least about 5% by weight of the at least one first component, or at least about 7% by weight of the at least one first component, or at least about 10% by weight of the at least one first component, or at least about 15% by weight of the at least one first component, or at least about 20% by weight of the at least one first component, or at least about 25% by weight of the at least one first component, or at least about 30% by weight of the at least one first component, based on the total weight of the product.
  • the product comprises about 0.1 wt % to about 30 wt % by weight of the at least one first component, or about 3 wt % to about 25 wt % by weight of the at least one first component, or about 5 wt % to about 20 wt % by weight of the at least one first component, or about 5 wt % to about 15 wt % by weight of the at least one first component, based on the total weight of the product.
  • the product comprises a functional material.
  • the functional material may be a functionally graded material (FGM).
  • the FGM may be a functionally graded composite material (FGCM).
  • the at least one first component is substantially soluble in the at least one first and/or second polymerizable component(s) and is substantially insoluble when the first and/or second polymerizable component(s) polymerizes.
  • the at least one first component may be selected from the group consisting of functional monomers, functional polymers, metal precursors, carbon nanotubes (CNT), graphene, metal alloy precursors, metalloid precursors, and combinations thereof.
  • the at least one first component is at least one functional monomer.
  • the at least one functional monomer may be fluorinated monomers such as, and without being limited thereto, fluorinated methacrylates.
  • the fluorinated functional monomers may contribute hydrophobic properties to the functional product.
  • the at least one polymerizable component is selectively polymerized (e.g. temperature/wavelength used) without substantially polymerizing the at least one functional monomer such that, for example, the functional monomer and the at least one polymer form at least two phases.
  • the functional monomer may polymerize somewhat with the at least one first and/or second polymerizable component(s); however, at least two phases form.
  • the at least one first component may be at least one functional polymer such as, and without being limited thereto, PEG.
  • the at least one polymerizable component is polymerized such that, for example, the functional polymer and the at least one first and/or second polymerizable component(s) form at least two phases.
  • the at least one first component is selected from the group consisting of metal salts, metal coordination compounds, organometallic compounds, organometalloid compounds, and combinations thereof. In typical embodiments, the at least one first component is selected from the group consisting of metal salts, metalloid salts, and combinations thereof. In certain embodiments, the at least one first component is selected from the group consisting of metal carboxylates, metalloid carboxylates, and combinations thereof.
  • the metal carboxylates may comprise from 1 to 20 carbon atoms, from 6 to 15 carbon atoms, or from 8 to 12 carbon atoms.
  • the carboxylate group of the metal carboxylates may be an alkanoate.
  • Examples of the at least one first component is selected from the group consisting of metal formate, metal acetate, metal propionate, metal butyrate, metal pentanoate, metal hexanoate, metal heptanoate, metal ethylhexanoate, metal behenate, metal benzoate, metal oleate, metal octanoate, metal nonanoate, metal decanoate, metal neodecanoate, metal hexafluoroacetylacetonate, metal phenylacetate, metal isobutyrylacetate, metal benzoylacetate, metal pivalate metal oxalate and combinations thereof.
  • the metal ion may be selected from the group consisting of Li + , Na + , K + , Rb + , Cs + , Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Sc 3+ , Sc 2+ , Sc + , Y 3+ , Y 2+ , Y + , Ti 4+ , Ti 3+ , Ti 2+ , Zr + , Zr 3+ , Zr 2+ , Hf 4+ , Hf 3+ , V 5+ , V 4+ , V 3+ , V 2+ , Nb 5+ , Nb 4+ , Nb 3+ , Nb 2+ , Ta 5+ , Ta 4+ , Ta 3+ , Ta 2+ , Cr 6+ , Cr + , Cr 4+ , Cr 3+ , Cr 2+ , Cr + , Cr, Mo 6+ , Mo 5 , Mo 4 , Mo 3
  • the at least one first component used in the method may be selected amongst nanoparticles and/or microparticles of at least one first component described herein.
  • the nanoparticles and/or microparticles may be metal precursors such as metal ions, metal salts, metal oxides, and/or metal complexes which may be convertible to metal.
  • the at least one first component may be any suitable inorganic particle that can separate into at least two phases from the at least one polymer, including nanoparticles and/or microparticles.
  • the nanoparticles or microparticles are composed of a metal or combinations of metals selected from metals of Groups IIA, IIIA, IIIB, IVB, VB, VIB, VIIB, VIIIB, IB or IIB of block d of the Periodic Table of Elements.
  • said metallic nanoparticles or microparticles are selected from Ba, Al, Sc, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Y, Zr, Nb, Tc, Ru, Mo, Rh, W, Au, Pt, Pd, Ag, Mn, Co, Cd, Hf, Ta, Re, Os, Al, Sn, In, Ga, Ir, and combinations thereof.
  • said metallic nanoparticles or microparticles are selected from Ba, Al, Cu, Ni, Ag, Au, Pt, Pd, Al, Fe, Co, Ti, Zn, In, Sn, Ga and combinations thereof. In yet other embodiments, said metallic nanoparticles or microparticles are selected from Al, Cu, Ni, Ti, Zn, Ag, and combinations thereof.
  • said metallic nanoparticles or microparticles are selected from Ag, Cu, and Ag and Cu nanoparticles. In other embodiments, the metallic nanoparticles or microparticles are Ag nanoparticles.
  • the at least one one first component is a metal precursor selected to be convertible in-situ into a metal by a chemical or electrochemical process. The metal precursor may also be reduced into corresponding metal by reduction of the metal precursor in the presence of a suitable photoinitiator and a radiation source. Thus, in some embodiments, the metal precursor is selected to be convertible into any one of the metals recited hereinabove. In some embodiments, the metal precursor is a salt form of any one metal recited hereinabove.
  • the metal salt is comprised of an inorganic or organic anion and an inorganic or organic cation.
  • the anion is inorganic.
  • inorganic anions include HO ⁇ , F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , NO 2 ⁇ , NO 3 ⁇ , ClO 4 ⁇ , SO 4 2 ⁇ , SO 3 ⁇ , PO 4 ⁇ and CO 3 2 ⁇ .
  • the anion is organic.
  • Non-limiting examples of organic anions include acetate (CH 3 COO ⁇ ), formate (HCOO ⁇ ), citrate (C 3 H 5 O(COO) 3 ⁇ 3 ) acetylacetonate, lactate (CH 3 CH(OH)COO ⁇ ), oxalate ((COO) 2 ⁇ 2 ) and any derivative of the aforementioned.
  • the metal salt is not a metal oxide.
  • the metal salt is a metal oxide.
  • the metal salt is a salt of copper.
  • Non-limiting examples of copper metal salts include copper formate, copper citrate, copper acetate, copper nitrate, copper acetylacetonate, copper perchlorate, copper chloride, copper sulfate, copper carbonate, copper hydroxide, copper sulfide or any other copper salt and the combinations thereof.
  • the metal salt is a salt of nickel.
  • nickel metal salts include nickel formate, nickel citrate, nickel acetate, nickel nitrate, nickel acetylacetonate, nickel perchlorate, nickel chloride, nickel sulfate, nickel carbonate, nickel hydroxide or any other nickel salts and the combinations thereof.
  • the metal salt is a salt of silver.
  • silver metal salts include silver carboxylates, silver lactate, silver nitrate, silver formate or any other silver salt and their mixtures.
  • silver carboxylates may be used and comprise a silver ion and an organic group containing a carboxylate group.
  • the carboxylate group may comprise from 1 to 20 carbon atoms, typically from 6 to 15 carbon atoms, more typically from 8 to 12 carbon atoms, for example 10 carbon atoms.
  • the carboxylate group is typically an alkanoate.
  • silver carboxylates are silver ethylhexanoate, silver neodecanoate, silver benzoate, silver phenylacetate, silver isobutyrylacetate, silver benzoylacetate, silver oxalate, silver pivalate and any combinations thereof.
  • silver neodecanoate is used.
  • the metal salt is selected from indium(II) acetate, indium(III) chloride, indium(III) nitrate; iron(II) chloride, iron(III) chloride, iron(II) acetate, gallium(III) acetylacetonate, gallium(II) chloride, gallium(II) chloride, gallium(II) nitrate; aluminum(III) chloride, aluminum(III) stearate; silver nitrate, silver chloride; dimethylzinc, diethylzinc, zinc chloride, tin(II) chloride, tin(IV) chloride, tin(II) acetylacetonate, tin(II) acetate; lead(II) acetate, lead(II) acetylacetonate, lead(II) chloride, lead(II) nitrate and PbS.
  • the at least one first component is selected from metal oxides such as those mentioned above, including nanoparticles and/or microparticles.
  • the metal oxides are selected from alumina, silica, barium titanate, transition metal oxides (e.g. zinc oxide, titanium oxide), and combinations thereof.
  • the at least one first component is selected from nanowires, microparticles, nanoparticles, or combinations thereof, including any of the suitable at least one first component mentioned herein.
  • the at least one first component comprises graphene.
  • the amount of the at least one first component may be any suitable amount.
  • the amount may be from about 0.1% to about 90% by weight based on the weight of the homogeneous mixture.
  • the amount of the at least one first component in the homogeneous mixture may be from about 0.1% to about 80% by weight, from about 0.1% to about 70% by weight, from about 0.1% to about 60% by weight, from about 0.1% to about 50% by weight, from about 0.1% to about 40% by weight, from about 0.1% to about 30% by weight, or from about 0.1% to about 20% by weight based on the weight of the homogeneous mixture.
  • additives may be added. Additives can be included, for example, to increase the solubility of the at least one first component in the at least one polymer component.
  • Various additives include, without being limited thereto, fillers, inhibitors, adhesion promoters, absorbers, dyes, pigments, anti-oxidants, carrier vehicles, heat stabilizers, flame retardants, thixotropic agents, flow control additives, dispersants, or combinations thereof.
  • extending fillers, reinforcing fillers, dispersants, or combinations thereof are added.
  • the additives can be microparticles or nanoparticles.
  • the formulation may be used to make the product described herein.
  • Examples 1-15 illustrate the various compositions and printing considerations for the making of conductive products (e.g. electrical devices) and non-conductive products (e.g. consumer products where it is desirable to have decorative coatings, such as jewellery).
  • conductive products e.g. electrical devices
  • non-conductive products e.g. consumer products where it is desirable to have decorative coatings, such as jewellery.
  • Comparative Example 1 Coating of SLA Printed Acrylate-Based Resin (FSL 3D) 3D Product with Ag Precursor i.e. Silver Neodecanoate+2-Ethyl-2-Oxazoline_7% Ag Metal
  • acrylate-based resin (Pegasus, FSL3D) was printed into cylinders about 1 cm in length and about 1 mm in diameter using a SLA printer and then immersed in a mixture of Ag precursor composed of about 4.44 g silver neodecanoate+about 20.084 ml 2-ethyl-2-oxazoline (7% Ag metal).
  • Coated 3D products were thermally sintered by using a reflow oven program to heat between about 200 and about 250° C. temperature for varying times under nitrogen with about 500 ppm oxygen.
  • Intense pulsed light sintering was also performed on thermally sintered samples with a Novacentrix PulseForge® 1300 system with sintering energies ranging from about 2.4 to about 3.1 J/cm 2 for about 3000 ⁇ s under ambient conditions.
  • Example 2 SLA Printed Ag Precursor+Acrylate-Based Resin (FSL 3D) (Silver Neodecanoate+2-Ethyl-2-Oxazoline_1.97% Ag Metal)
  • a resin was formulated by mixing about 6.25 g silver neodecanoate+about 1.38 ml 2-ethyl-2-oxazoline+about 114.99 g commercial acrylate-based resin (Pegasus, FSL3D) to make final formulation with about 1.97 wt. % silver content.
  • the resin was printed into cylinders about 1 cm in length and about 1 mm in diameter.
  • the 3D products were thermally sintered by using a reflow oven program to heat from about 200 to about 250° C. temperature for varying times under nitrogen with about 500 ppm oxygen.
  • Intense pulsed light sintering was also performed on thermally sintered samples with a Novacentrix PulseForge® 1300 system with sintering energies ranging from about 2.4 to about 3.1 J/cm 2 for about 3000 s under ambient conditions.
  • Example 3 SLA Printed Ag Precursor+Acrylate-Based Resin (FSL 3D) (Silver Neodecanoate+2-Ethyl-2-Oxazoline_3.84% Ag Metal)
  • a resin was formulated by mixing about 12.5 g silver neodecanoate+about 2.76 ml 2-ethyl-2-oxazoline+about 107.36 g commercial acrylate-based resin (Pegasus, FSL3D) to make final formulation with about 3.84 wt. % silver content.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered from about 200 to about 250° C. temperature ranges (program) by varying time using reflow oven under nitrogen with about 500 ppm oxygen.
  • Intense pulsed light sintering was also performed on thermally sintered samples with a Novacentrix PulseForge® 1300 system with sintering energies ranging from about 2.4 to about 3.1 J/cm 2 for about 3000 s under ambient conditions.
  • Example 4 SLA Printed Ag Precursor+Acrylate-Based Resin (FSL 3D) (Silver Neodecanoate+2-Ethyl-2-Oxazoline_7% Ag Metal)
  • a resin was formulated by mixing about 22.2 g silver neodecanoate+about 5.03 ml 2-ethyl-2-oxazoline+about 94.89 g commercial acrylate-based resin (Pegasus, FSL3D) to make final formulation with about 7 wt. % silver content.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered from about 200 to about 250° C. temperature ranges (program) by varying time using reflow oven under nitrogen with about 500 ppm oxygen.
  • Intense pulsed light sintering was also performed on thermally sintered samples with a Novacentrix PulseForge® 1300 system with sintering energies ranging from about 2.4 to about 3.1 J/cm 2 for about 3000 s under ambient conditions.
  • Example 5 SLA Printed Ag Precursor+Acrylate-Based Resin (FSL 3D) (Silver Neodecanoate+2-Ethyl-2-Oxazoline_7.9% Ag Metal)
  • a resin was formulated by mixing about 25 g silver neodecanoate+about 5.52 ml 2-ethyl-2-oxazoline+about 92.1 g commercial acrylate-based resin (Pegasus, FSL3D) to make final formulation with about 7.9 wt. % silver content.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered from about 200 to about 250° C. temperature ranges (program) by varying time using reflow oven under nitrogen with about 500 ppm oxygen.
  • Intense pulsed light sintering was also performed on thermally sintered samples with a Novacentrix PulseForge® 1300 system with sintering energies ranging from about 2.4 to about 3.1 J/cm 2 for about 3000 s under ambient conditions.
  • Example 6 SLA Printed Ag Precursor+Acrylate-Based Resin (FSL 3D) (Silver Neodecanoate+2-Ethyl-2-Oxazoline_9.85% Ag Metal)
  • a resin was formulated by mixing about 31.25 g silver neodecanoate+about 6.9 ml 2-ethyl-2-oxazoline+about 84.47 g commercial acrylate-based resin (Pegasus, FSL3D) to make final formulation with about 9.85 wt. % silver content.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered from about 200 to about 250° C. temperature ranges (program) by varying time using reflow oven under nitrogen with about 500 ppm oxygen.
  • Intense pulsed light sintering was also performed on thermally sintered samples with a Novacentrix PulseForge® 1300 system with sintering energies ranging from about 2.4 to about 3.1 J/cm 2 for about 3000 s under ambient conditions.
  • Example 7 SLA Printed Ag Salt+Acrylate-Based Resin (FSL 3D) (Silver Neodecanoate_7% Ag Metal)
  • a resin was formulated by mixing about 22.2 g silver neodecanoate+about 100.42 g commercial acrylate-based resin (Pegasus, FSL3D) to make final formulation with about 7 wt. % silver content.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered between about 200 to about 250° C. temperature ranges (program) by varying time using reflow oven under nitrogen with about 500 ppm oxygen.
  • Intense pulsed light sintering was also performed on thermally sintered samples with a Novacentrix PulseForge® 1300 system with sintering energies ranging from about 2.4 to about 3.1 J/cm 2 for about 3000 s under ambient conditions.
  • viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial.
  • the combined mixture was then vortex mixed for 2 minutes at about 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered from about 240 to about 300° C. temperature ranges (program) for about 1 hour using reflow oven under nitrogen.
  • the combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • Example 10 SLA Printed Ag Precursor+Acrylate-Based Resin (FSL 3D) (Silver Nitrate+2-Ethyl-2-Oxazoline_7% Ag Metal)
  • a resin was formulated by mixing about 13.5 g silver nitrate+about 6.04 ml 2-ethyl-2-oxazoline+about 103.73 g commercial acrylate-based resin (Pegasus, FSL3D) to make final formulation with about 7 wt. % silver content.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered from about 200 to about 250° C. temperature ranges (program) by varying time using reflow oven under nitrogen with about 500 ppm oxygen.
  • Intense pulsed light sintering was also performed on thermally sintered samples with a Novacentrix PulseForge® 1300 system with sintering energies ranging from about 2.4 to about 3.1 J/cm 2 for about 3000 s under ambient conditions.
  • Example 11 SLA Printed Ag Precursor+Acrylate-Based Resin (FSL 3D) (Silver Acetate+2-Ethyl-2-Oxazoline_7% Ag Metal)
  • a resin was formulated by mixing about 13.3 g silver acetate+about 8.05 ml 2-ethyl-2-oxazoline+about 101.29 g commercial acrylate-based resin (Pegasus, FSL3D) to make final formulation with about 7 wt. % silver content.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered from about 200 to about 250° C. temperature ranges (program) by varying time using reflow oven under nitrogen with about 500 ppm oxygen.
  • Intense pulsed light sintering was also performed on thermally sintered samples with a Novacentrix PulseForge® 1300 system with sintering energies ranging from about 2.4 to about 3.1 J/cm 2 for about 3000 s under ambient conditions.
  • Example 12 SLA Printed Cu Precursor+Acrylate-Based Resin (FSL 3D) (Cu Formate+_7% Cu Metal)
  • a resin was formulated by mixing about 23.18 g copper formate hydrate+about 10.3 ml 3-(diethylamino)-1 2-propanediol+about 89.15 g commercial acrylate-based resin (Pegasus, FSL3D) to make final formulation with about 7 wt. % Cu content.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered from about 200 to about 250° C. temperature ranges (program) by varying time using reflow oven under nitrogen with about 500 ppm oxygen.
  • Intense pulsed light sintering was also performed on thermally sintered samples with a Novacentrix PulseForge® 1300 system with sintering energies ranging from about 2.4 to about 3.1 J/cm 2 for about 3000 s under ambient conditions.
  • Example 13 SLA Printed Graphene+Acrylate-Based Resin (FSL 3D) (0.05% Graphene)
  • a resin was formulated by mixing about 0.05 g graphene (N002-PDR-HD Angstrom Materials)+about 1.25 g dispersant BYK 180+about 98.7 g commercial acrylate-based resin (Pegasus, FSL3D) to make final formulation with about 0.05 wt. % graphene content.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 200° C. (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • Example 14 SLA Printed Graphene+Acrylate-Based Resin (FSL 3D) (0.4% Graphene)
  • a resin was formulated by mixing about 0.4 g graphene (N002-PDR-HD Angstrom Materials)+about 10 g dispersant BYK 180+about 89.6 g commercial acrylate-based resin (Pegasus, FSL3D) to make final formulation with 0.4 wt. % graphene content.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 200° C. (program) for 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • Example 15 SLA Printing of Hydrophobic Tiles Using Fluorinated Monomers
  • Resins containing various % weight of 1H,1H-perfluorooctyl methacrylate, 2-ethylhexyl acrylate and trimethylolpropane triacrylate were prepared according to Table 1.
  • a 2% wt. fraction of ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate as photoinitiator was used in all resins.
  • the resins were SLA printed into tiles about 1 cm ⁇ about 1 cm ⁇ about 0.2 cm in size using a Peopoly Moai SLA 3D printer with a about 210 mW laser and laser setting of about 75. Once printed, the tiles were removed from the build plate and washed in ethanol.
  • the resins were also drop casted onto glass slides, UV-cured using a Dymax Light Curing System (Model 5000 Flood) and washed with ethanol.
  • the contact angles of the 3D printed tiles and the UV-cured films were measured using a 5 ⁇ L drop of water.
  • TGA analysis of resin and functional material resins were performed via a TGA A588 TGA-IR module.
  • 3D products were thermally sintered at about 200 to about 250° C. temperature (program) ranges by varying time using reflow oven under nitrogen with about 500 ppm oxygen.
  • Intense pulsed light sintering photonic curing was also performed on thermally sintered samples with a Novacentrix PulseForge® 1300 system with sintering energies ranging from about 2.4 to about 3.1 J/cm2 for about 3000 s under ambient conditions.
  • Characterization of 3D products A two-point probe method was used to measure the resistance of the 3D printed products using a multimeter after thermal and photonic sintering. Scanning electron microscopy (SEM) images were acquired with a Hitachi SU3500.
  • Example Functional No. component Resin Processing Comment 1 (comparative silver Acrylate-based 1) SLA printing Non- example) neodecanoate + resin of resin, conducting 2-ethyl-2- (FSL 3D) 2) coating of products oxazoline functional (7% Ag metal) component 3) thermal sintering 2
  • FIGS. 2 A, 2 B, and 2 C Examples of 3D printed products are shown in FIGS. 2 A, 2 B, and 2 C .
  • FIGS. 3 A- 3 C SEM images of 3D printed cylinders of Example 4 are shown in FIGS. 3 A- 3 C .
  • the cylinders were about 1 cm in length and diameters of a) about 350 mm, b) about 500 mm and c) about 1500 mm.
  • the images of the cross-sections were taken near the surface of the cylinder to demonstrate the phase separation of silver and polymer. The silver appears as the bright areas and the polymer as the dark areas.
  • the thickness of the functional coating increases.
  • the schematic in FIG. 3 D provides a perspective of where the SEM images where taken on the cylinders (red circle, top left at the interface of the surface layer and rest of the product).
  • Concentration gradient in 3D printed product of Example 4 Cross-sectional SEM images of the interface of a 3D printed product are shown in FIGS. 4 A and 4 B . The images show a top layer of silver formed on the polymer core. Within the polymer core, a concentration gradient of silver nanoparticles was observed, with the concentration of silver (bright areas) decreasing with distance away from the surface of the product.
  • the residual mass of the SLA 3D product was about 9.66% while the initial formulation predicted a residual mass of about 7.88% (silver content) ( FIG. 5 ).
  • the molecular silver ink formulations were prepared by first dissolving silver salt in an amine. Subsequently, commercial acrylate-based resin (Pegasus, FSL3D) or flexible resin (photocentric 3D) was added in to the silver/amine complex to form the final formulation with about 2 to about 10 wt % silver content based on the total weight of the formulation (see Table 5 below).
  • commercial acrylate-based resin Pegasus, FSL3D
  • flexible resin photocentric 3D
  • FIGS. 6 A and 6 B Optical images of 3D printed cylinders of Example 15 are shown in FIGS. 6 A and 6 B .
  • FIG. 6 B shows the increase in the contact angle of the tiles with the addition of a fluorinated monomer to the resin, relative to the contact angles shown in FIG. 6 A .
  • FIG. 7 shows that using the same resin, SLA printed tiles generate surfaces with higher contact angles than those UV-cured as a film.
  • Examples 16-57 provide additional embodiments of formulations and printing conditions which resulted in functional coatings, graded compositions, and composites.
  • the 3D printing SLA resins have three components: mono-functional monomers, di-, tri- and tetra-functional cross-linking agents and a photoinitiator.
  • mono-functional monomers di-, tri- and tetra-functional cross-linking agents
  • a photoinitiator Various cross-linking agents composed of different reactive end groups and inner subunits were tested. Higher cross-linking percentage led to the prints having greater tensile strength with graded and composite structure products, and lower cross-linking percentages usually having lower resistivities with functionally coated phase separated products.
  • the attractive and repulsive forces (hydrophobic/hydrophilic interactions) between components were leveraged to control the placement of functional components.
  • the components had similar hydrophilic or hydrophobic properties, the components had less of a driving force to phase separate upon polymerization.
  • the functional component had a larger driving force to separate from the composition (e.g. polymerizing monomer/cross-linking agent mixture).
  • the resin formulations shown in the Tables provided useful products without the listed functional components.
  • the resulting product may be used as a scaffold for receiving metallic functional components (e.g. through electroplating) and as barrier type coatings (e.g. hydrophobic), dielectrics or insulating material, and may be selected for the desired flexibility and strength needed in the final product.
  • ethyleneglycol diacrylate about 8.4 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial.
  • the mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds.
  • about 2.5 g of silver neodecanoate were dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds.
  • viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial.
  • the combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial.
  • the combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial.
  • the combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial.
  • the combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial.
  • the combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial.
  • the combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial.
  • the combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial.
  • the combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial.
  • the combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial.
  • the combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • the combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial.
  • the combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial.
  • the combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial.
  • the combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • the combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial.
  • the combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial.
  • the combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial.
  • the combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial.
  • the combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial.
  • the combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial.
  • the combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial.
  • the combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial.
  • the combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial.
  • the combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial.
  • the combined mixture was then vortex mixed for 2 minutes at 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • the combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial.
  • the combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial.
  • the combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial.
  • the combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial.
  • the combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial.
  • the combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial.
  • the combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • Example 48 Ag Precursor+(50% 1,6-Hexanediol Diacrylate, 49% EGMEA) Resin
  • viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial.
  • the combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • viscous silver solution was added about 9.21 g of the acrylate mixture from the first vial.
  • the combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm.
  • the resin was SLA printed into cylinders about 1 cm in length and about 1 mm in diameter and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • FIG. 17 shows SEM images of 3D TiO 2 products printed without toluene (a, b and c) and with toluene (d, e and f) and
  • FIG. 18 shows wt % of TiO 2 as a function of distance from the surface of the 3D TiO 2 products. Products without toluene had a wider TiO 2 wt % distribution.
  • FIG. 19 shows SEM images of 3D Barium Strontium Titanate (BST) product.
  • FIG. 20 shows a) SEM images of the cross-section of a printed cylinder with iron oxide nanoparticles. The nanoparticles appear as bright areas in the SEM; Energy dispersion spectroscopy (EDS) analysis of the SEM mapping out b) carbon and c) iron in the sample.
  • EDS Energy dispersion spectroscopy
  • TPO-L sintering 0.88 ⁇ /cm 18 AgND + EtOxa 25% wt. EGDA, 27 1) SLA printing Conducting (7.9% Ag metal) 74% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 1 ⁇ /cm 21 AgND + EtOxa 15% wt. PEGDA250, 11 1) SLA printing Conducting (7.9% Ag metal) 84% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 4.3 ⁇ /cm 22 AgND + EtOxa 20% wt. PEGDA250, 14 1) SLA printing Conducting (7.9% Ag metal) 79% wt. EHA, 2) thermal products 1% wt.
  • TPO-L sintering 1.36 ⁇ /cm 23 AgND + EtOxa 25% wt. PEGDA250, 20 1) SLA printing Conducting (7.9% Ag metal) 74% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 2 ⁇ /cm 24 AgND + EtOxa 35% wt. PEGDA250, 29 1) SLA printing Conducting (7.9% Ag metal) 64% wt. EHA, 2) thermal products 1% wt TPO-L sintering 1.4 ⁇ /cm 27 AgND + EtOxa 25% wt. TEGDA, 18 1) SLA printing Conducting (7.9% Ag metal) 74% wt. EHA, 2) thermal products 1% wt.
  • TPO-L sintering 1.85 ⁇ /cm 28 AgND + EtOxa 35% wt. TEGDA, 26 1) SLA printing Conducting (7.9% Ag metal) 64% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 1.28 ⁇ /cm 31 AgND + EtOxa 25% wt. PEGDA575, 12 1) SLA printing Conducting (7.9% Ag metal) 74% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 4.96 ⁇ /cm 32 AgND + EtOxa 35% wt. PEGDA575, 20 1) SLA printing Conducting (7.9% Ag metal) 64% wt.
  • EHA 2) thermal products 1% wt. TPO-L sintering 2.16 ⁇ /cm 33 AgND + EtOxa 45% wt. PEGDA575, 28 1) SLA printing Conducting (7.9% Ag metal) 54% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 4.24 ⁇ /cm 34 AgND + EtOxa 50% wt. PEGDA575, 33 1) SLA printing Conducting (7.9% Ag metal) 49% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 7.42 ⁇ /cm 36 AgND + EtOxa 25% wt. PEG700, 11 1) SLA printing Conducting (7.9% Ag metal) 74% wt.
  • EHA 2) thermal products 1% wt. TPO-L sintering 2.23 ⁇ /cm 37 AgND + EtOxa 35% wt. PEGDA700, 18 1) SLA printing Conducting (7.9% Ag metal) 64% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 2.64 ⁇ /cm 42 AgND + EtOxa 35% wt. BDDA, 33 1) SLA Conducting (7.9% Ag metal) 64% wt. EHA, printing products 1% TPO-L 2) thermal 1.32 ⁇ /cm sintering 45 AgND + EtOxa 35% wt. HDDA, 31 1) SLA printing Conducting (7.9% Ag metal) 64% wt.
  • EHA 2) thermal products 1% wt. TPO-L sintering 0.94 ⁇ /cm 50 2.5% TiO 2 functionalized 35% wt. PEGDA250, 29 1) SLA printing Functional with 2- 64% wt. EHA, 2) thermal products methoxy(polyethyleneoxy)propyl 1% wt. TPO-L sintering with phase trimethoxysilane separation (e.g. coated) 51 2.5% TiO 2 functionalized 35% wt. PEGDA250, 29 1) SLA printing Functional with 2- 61.7% wt. EHA, 2) thermal products methoxy(polyethyleneoxy)propyl 1% wt.
  • TPO-L sintering with phase trimethoxysilane toluene separation 52 2.5% Barium Strontium 35% wt. PEGDA250, 29 1) SLA printing Functional Titanate (BST) 64% wt. EHA, 2) thermal products functionalized with 2- 1% wt. TPO-L sintering with phase methoxy(polyethyleneoxy)propyl separation trimethoxysilane 53 2.5% Iron oxide 35% wt. PEGDA250, 29 1) SLA printing Functional 64% wt. EHA, 2) thermal products 1% wt. TPO-L sintering with phase separation
  • EHA 2) thermal Conducting 1% wt. TPO-L sintering products 25 AgND + EtOxa 50% wt. PEGDA250, 43 1) SLA printing Conducting (7.9% Ag metal) 49% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 7.6 ⁇ /cm 29 AgND + EtOxa 50% wt. TEGDA, 40 1) SLA printing Conducting (7.9% Ag metal) 49% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 13.16 ⁇ /cm 35 AgND + EtOxa 65% wt. PEGDA575, 50 1) SLA printing Conducting (7.9% Ag metal) 34% wt.
  • EHA 2) thermal products 1% wt. TPO-L sintering 21.04 ⁇ /cm 38 AgND + EtOxa 50% wt. PEGDA700, 32 1) SLA printing Conducting (7.9% Ag metal) 49% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 12.55 ⁇ /cm 39 AgND + EtOxa 60% wt. PEGDA700, 42 1) SLA printing Conducting (7.9% Ag metal) 39% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 28.44 ⁇ /cm 40 AgND + EtOxa 80% wt.
  • HDDA 45 1) SLA printing Conducting (7.9% Ag metal) 49% wt. EHA, 2) thermal products 1% wt. TPO-L sintering 2.9 ⁇ /cm 47 AgND + EtOxa 65% wt. HDDA, 65 1) SLA printing Conducting (7.9% Ag metal) 34% wt. EHA, 2) thermal products 1% TPO-L sintering 37.4 ⁇ /cm 48 AgND + EtOxa 50% wt. HDDA, 50 1) SLA printing Conducting (7.9% Ag metal) 49% wt. EGMEA, 2) thermal products 1% wt. TPO-L sintering 112 ⁇ /cm 49 AgND + EtOxa 25% wt. DTMPTA, 16 1) SLA printing Conducting (7.9% Ag metal) 74% wt. EHA, 2) thermal products 1% wt. TPO-L sintering K ⁇ /cm
  • the morphology of the printed product may depend on the concentration of cross-linking agent.
  • non-polymerizing functional precursor component was silver neodecanoate, it may be converted to silver post printing by heating to elevated temperatures.
  • non-polymerizing functional nanoparticles such as TiO 2 , F 2 O 3 and ZnO.
  • FIG. 8 shows the amount of silver (% wt) at the surface decreased with increased concentration of cross-linking agent.
  • the concentration of silver at the surface can determine the resistance value of the printed product.
  • FIG. 10 illustrates the change in the concentration of silver in a 3D printed cylinder depending on the amount of EGDA cross-linking agent.
  • Example 54 3D Printed Strain Sensors
  • a resin consisting of about 50% PEGDA575, about 49% EHA was prepared by mixing about 5.0 g of polyethyleneglycol diacrylate (Mn 575), about 4.9 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds. The resin was SLA printed then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • a resin consisting of about 35% PEGDA250, about 64% EHA was prepared by mixing about 3.5 g of polyethyleneglycol diacrylate Mn 250, about 6.4 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate into a 20 mL scintillation vial.
  • the mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds.
  • the resin was SLA printed then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • the final resin composition was prepared by mixing about 2.5 g of silver neodecanoate dissolved in about 0.552 mL of 2-ethyl-2-oxazoline using a planetary mixer at about 2000 rpm for about 4 min followed by about 2200 rpm for about 30 seconds. To the yellow, viscous silver solution was added about 9.21 g of the acrylate mixed resin (about 7.5 ml (about 50% PEGDA575, about 49% EHA)+about 2.5 ml (about 35% PEGDA250, about 64% EHA)). The combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm. The resin was SLA printed into 3D truss products and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • Example 55 3D Printed Products with Multimaterial Resin of Silver Precursor, Graphene and Acrylate Resin (7.88% Ag+0.2% Graphene Products Using Mixed Resin (7.5 ml (50% PEGDA575, 49% EHA)+2.5 ml (35% PEGDA250, 64% EHA))
  • Conducting structures ⁇ 5-10 ⁇ /cm resistance, silver is phase separated (e.g. coated)
  • Example 56 3D Printed Products with Multimaterial Resin of Silver Precursor, Graphene, Barium Strontium Titanate and Acrylate Resin (7.88% Ag+0.2% Graphene+0.5% BST Products Using Mixed Resin (7.5 ml (50% PEGDA575, 49% EHA)+2.5 ml (35% PEGDA250, 64% EHA))
  • the combined mixture was then vortex mixed for about 2 minutes at about 3200 rpm and sonicated for about 15 mins.
  • the resin was SLA printed into 3D truss products and then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • Conducting structures ⁇ 5-10 ⁇ /cm resistance, silver is phase separated
  • the products formed a graded composition with a high concentration of silver particles in the polymer near the surface of the product and decreasing in concentration away from the surface of the product.
  • the morphology of silver particles made it possible to generate a strain sensor as described in FIG. 11 .
  • the silver nanoparticles embedded in the product make contact increasing the electrical conductivity of the sample as shown in FIG. 12 .
  • Example 57 Evaluation of the Antibacterial Behaviors of 3D Printed Ag Product and the Control Resin Product without Ag Through Halo Inhibition Zone Tests
  • nano-silver particles have been applied to a wide range of health-care products, such as burn dressings, water purification systems, and dental and medical devices.
  • health-care products such as burn dressings, water purification systems, and dental and medical devices.
  • silver incorporated in orthodontic brackets will be useful in dentistry.
  • 3D printed functional products of this kind can be produced according to the formulations and methods of the present disclosure.
  • Control Product (about 35% PEGDA575, about 64% EHA)
  • Resin about 3.5 g of polyethyleneglycol diacrylate Mn 575, about 6.4 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial.
  • the mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds.
  • the resin was SLA printed then thermally sintered at about 250° C. temperature (program) for about 1 hour using reflow oven under nitrogen with about 500 ppm oxygen.
  • Ag Precursor+(about 35% PEGDA575, about 64% EHA) Resin about 3.5 g of polyethyleneglycol diacrylate Mn 575, about 6.4 g of 2-ethylhexylacrylate, and about 0.1 g of Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate were added into a 20 mL scintillation vial. The mixture was mixed using a vortex mixer at about 3200 rpm for about 30 seconds.
  • FIGS. 13 - 16 The procedure used to conduct the antimicrobial tests and obtain the results shown in FIGS. 13 - 16 are described in Balouiri et al. Journal of Pharmaceutical Analysis 6 (2016) 71-79 and Belkhair et al. RSC Adv., 2015, 5, 40932-40939, both of which are herein incorporated by reference in their entirety.
  • FIGS. 13 there is bacterial growth inhibition in the Ag products compared to controls that do not contain Ag in the zones that arise in proximity to scaffolds.
  • FIG. 13 shows evaluation of the antibacterial behaviors of a 3D printed Ag object and a control resin object without Ag through halo inhibition zone tests on E. coli plated agar plates. In the proximity of the 3D objects with Ag, growth is inhibited due to Ag leaching.
  • FIG. 13 shows evaluation of the antibacterial behaviors of a 3D printed Ag object and a control resin object without Ag through halo inhibition zone tests on E. coli plated agar plates. In the proximity of the 3D objects with Ag,
  • FIG. 14 shows bacterial growth on the 3D object with and without Ag in culture.
  • FIG. 15 shows bacterial growth kinetics with the 3D object with and without Ag in a liquid culture.
  • FIG. 16 shows bacterial growth kinetics of the supernatant from the FIG. 15 study in liquid culture without 3D objects.
  • the Ag object shows bacterial growth inhibition as reflected by the lower absorbance values.
  • the control provided the highest absorbance readings over time.
  • Example 58 SLA Printing of Hydrophobic Tiles Using Fluorinated Monomers
  • Molecular coatings can be generated from slow polymerizing monomers (methacrylates) in a resin containing mostly fast polymerizing acrylates.
  • fluorinated methacrylates were used to make a fluorinated hydrophobic coating from a resin containing primarily non-fluorinated acrylates. The resulting products are useful for anti-fouling/anti-microbial and de-icing applications.
  • the results in FIG. 21 are the contact angles of tiles printed from the photoresins containing a fluorinated monomer of varying concentrations.
  • the results show that as the weight fraction of fluorinated monomer increases, the contact angles of the surfaces of the tiles increases.
  • the photoresins with fluorinated methacrylates i.e. 1H, 1H-perfluorooctyl methacrylate and 2,2,3,4,4,4-hexafluorobutyl methacrylate
  • this result may be due to the lower polymerization rates of methacrylates in comparison to acrylates that cause these monomers to polymerize at later stages during the printing process and cause these monomers to concentrate at the surface of the product.
  • FIG. 22 illustrates the changes in contact angles as layers of polymers are removed for a tile printed using about 20% wt. 2,2,3,4,4,4-hexafluorobutyl methacrylate.
  • the results show that the contact angle of the tile decreased as a function of the depth of the tile, an indication that the fluorinated component was concentrated at the surface of the tile.
  • the dimensions of the spaces and support bridges varied depending on resolution of the photopolymer and SLA printer.
  • the structure was sonicated three times in isopropanol for about 10 min to remove excess resin from the spaces in between and surrounding the structure and then dried.
  • the structure was UV cured for about 5 min in a second stage to ensure complete polymerization.
  • the second set of thermal or UV curable monomer(s)/crosslinker(s) were weighed at appropriate ratios to be cured (about 2.5 g of epoxypropoxypropyl terminated polydimtheylsiloxane and about 2.5 g of aminopropyl terminated polydimethylsiloxane).
  • Example 59a SLA Printing of Products—Infiltration of One Photopolymer
  • the structure was sonicated three times in isopropanol for about 10 min to remove excess resin from the spaces in between and surrounding the structure and then dried.
  • the second set of thermal curable resin was mixed, containing 5.0 g of epoxypropoxypropyl terminated polydimtheylsiloxane and 5.0 g of aminopropyl terminated polydimethylsiloxane. This was mixed by using a vortex mixer for about 30 s.
  • the spaces in the 3D printed structure were filled by submerging the structure in the second set of monomer(s)/crosslinker(s) mixture and then thermally cured at about 160° C. for about 2.5 hours. The results can be found in FIG.
  • a-d) show top and e-f) show side images of the custom designed structure of platelets separated by spaces and held together with support bridges using a stereolithographic printer.
  • a, c, and e) show the structure after printing and before infiltration with the thermal curable resin.
  • b, d, f) show the structure after infiltration and thermal curing of the second resin.
  • Examples 60a-60b SLA Printing of Products—Phase Separation with One Photopolymer and a First Component (e.g. Functional Material)
  • Example 60a The commercial Form Labs Ceramic resin (FLCEWH01, Formlabs, contains acrylated monomers, photoinitiator(s), ⁇ 1 wt % additives, silica filler) was shaken for about 1 min, which includes a photoinitiator and functional material. The homogeneous mixture was used to produce a similar 3D printed structure as above for the Infiltration of One Photopolymer method. The structure was washed three times in isopropanol to remove residual resin, then UV cured for about 5 min to ensure complete polymerization. The preliminary results can be found in FIG. 26 .
  • Example 60b The First Set of Photopolymerizing Monomer(s)/Crosslinker(s)/Functional
  • the material(s) contains about a 1:1 weight ratio of ethylene glycol phenyl ether acrylate and 1,6-hexanediol diacrylate, which was weighed in a 20 mL scintillation vial (4.9 g of each monomer and crosslinker). To the mixture, about 2 wt % diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO, about 0.2 g)) was added as the photoinitiator. The functional material, hydride terminated polydimethylsiloxane, about 7 to about 10 cSt, was then added at about 10 wt % of the entire resin mixture (about 9:1 weight ratio of first set to functional material).
  • TPO diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide
  • the mixture was dissolved using a planetary mixer at about 2000 rpm for about 30 min followed by about 2200 rpm for about 30 s so that some of the polydimethylsiloxane dissolves in the monomer resin with the mixing.
  • the structure was immediately UV cured after printing for about 5 min to ensure complete polymerization. The preliminary results can be found in FIGS. 27 - 29 and Table 12.
  • Example 61 SLA Printing of Products—Phase Separation with One Photopolymer and a Thermal Curable Polymer
  • the first set of faster photopolymerizing monomer(s)/crosslinker(s)/functional material(s) is added in a weight ratio for the optimal chemical (reaction rate, gelation rate, miscibility, etc.) and physical properties in a 20 mL scintillation vial.
  • about 0.5 to about 3 weight percent photoinitiator is added to the mixture.
  • the second set of monomer(s)/crosslinker(s)/functional material(s) with different thermodynamic miscibility and/or an orthogonal polymerization mechanism are weighed out in a 20 mL scintillation vial in appropriate ratios for the desired chemical (reaction rate, gelation rate, miscibility, etc.) and physical properties.
  • the two resin sets are added together in the appropriate ratio for phase separation and desired physical properties.
  • the mixture is dissolved using a planetary mixer at about 2000 rpm for about 30 min followed by about 2200 rpm for about 30 s.
  • Phase separation of the second polymer resin into the spaces in between or confined within the first polymer printed structure may occur due to different thermodynamic miscibilities (e.g. monomers are polar vs. non-polar, aromatic vs. aliphatic, aliphatic vs. polydimethylsiloxane-functionalized).
  • the final structure is thermally cured using a reflow oven (to polymerize the second polymerizable component) followed by UV curing for about 5 min to ensure complete polymerization.
  • the first set of faster photopolymerizing monomer(s)/crosslinker(s)/functional material(s) is added in a weight ratio for the optimal chemical (reaction rate, gelation rate, miscibility, etc.) and physical properties in a 20 mL scintillation vial.
  • about 0.5 to about 3 weight percent photoinitiator is added to the mixture.
  • the second set of monomer(s)/crosslinker(s)/functional material(s) with slower kinetics or different thermodynamic miscibility and/or an orthogonal polymerization mechanism were weighed out in a 20 mL scintillation vial in appropriate ratios for the desired chemical (reaction rate, gelation rate, miscibility, etc.) and physical properties.
  • a second photoinitiator that initiates an orthogonal polymerization mechanism to the first set, may be added at about 0.5 to about 3 weight percent of the second set resin.
  • the two resin sets are added together in the appropriate ratio for phase separation and desired physical properties.
  • the mixture is dissolved using a planetary mixer at about 2000 rpm for about 30 min followed by about 2200 rpm for about 30 s.
  • Phase separation of the second polymer resin into the spaces in between the first polymer printed structure may occur due to kinetics (slower photopolymerization) and/or different thermodynamic miscibilities (e.g. monomers are polar vs. non-polar, aromatic vs. aliphatic, aliphatic vs. polydimethylsiloxane-functionalized).
  • the final structure is washed three times in isopropanol by sonicating for about 10 min to remove residual resin, then UV cured for about 5 min to ensure complete polymerization.
  • Example 62a SLA Printing of Products—Phase Separation with Two Photopolymers
  • the first set of faster photopolymerizing resin containing 4.95 g of ethylene glycol phenyl ether acrylate and 4.95 g of 1,6-hexanediol diacrylate is added to a 20 mL scintillation vial.
  • 0.1 g (1 wt %) photoinitiator, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide is added.
  • the mixture was dissolved using a planetary mixer at about 2000 rpm for about 30 min followed by about 2200 rpm for about 30 s.
  • the second set of resin with slower kinetics, different thermodynamic miscibility, and an orthogonal polymerization mechanism were weighed out in a 20 mL scintillation vial and contained 4.9 g of epoxypropoxypropyl terminated polydimethylsiloxane, 8-11 cSt.
  • a second photoinitiator and co-initiator, 0.05 g of triarylsulfonium hexafluoroantimonate salts, mixed and 0.05 g of isopropyl-thioxanthone, that initiates an orthogonal polymerization mechanism to the first set was added.
  • the mixture was dissolved using a planetary mixer at about 2000 rpm for about 30 min followed by about 2200 rpm for about 30 s.
  • the first and second resins were mixed in a weight ratio of 9:1.
  • the mixture was dissolved using a planetary mixer at about 2000 rpm for about 30 min followed by about 2200 rpm for about 30 s.
  • the resin was used to print a custom designed structure using a stereolithographic printer ( FIG. 27 a ).
  • the final structure is washed three times in isopropanol by sonicating for about 10 min to remove residual resin, then UV cured for about 5 min to ensure complete polymerization.
  • the phase separation results can be found in FIG. 31 where, as shown in panel a) of FIG.
  • Panel b) of FIG. 31 shows a Raman spectroscopy mapping, which shows the interface between the top and bottom of the structure with respect to the change in —C—H peak intensity relative to the baseline at ⁇ 2920 cm ⁇ 1 .

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