A method of forming the body portion of a three-dimensional object from a polymerizable liquid by the process of continuous liquid interface printing is described. The body portion has a plurality of contiguous segments, and the process includes advancing a carrier for the object away from a build surface while irradiating a build region between the carrier and build surface in a pattern of advancing and irradiating defined by an operating mode. In the present invention, the operating mode is changed at least once during the formation of the body portion for different contiguous segments of the body portion.

A method of forming a three-dimensional object of polyurethane, polyurea, or copolymer thereof is carried out by: (a) providing a carrier and an optically transparent member having a build surface, the carrier and the build surface defining a build region therebetween; (b) filling the build region with a polymerizable liquid, the polymerizable liquid including at least one of: (i) a blocked or reactive blocked prepolymer, (ii) a blocked or reactive blocked diisocyanate, or (iii) a blocked or reactive blocked diisocyanate chain extender; (c) irradiating the build region with light through the optically transparent member to form a solid blocked polymer scaffold and advancing the carrier away from the build surface to form a three-dimensional intermediate having the same shape as, or a shape to be imparted to, the three-dimensional object, with the intermediate containing the chain extender; and then (d) heating or microwave irradiating the three-dimensional intermediate sufficiently to form from the three-dimensional intermediate the three-dimensional object of polyurethane, polyurea, or copolymer thereof.

A method of forming a three-dimensional object is carried out by: (a) providing a carrier and an optically transparent member having a build surface, the carrier and the build surface defining a build region therebetween; (b) filling the build region with a polymerizable liquid, the polymerizable liquid including a mixture of (i) a light polymerizable liquid first component, and (ii) a second solidifiable component that is different from the first component; (c) irradiating the build region with light through the optically transparent member to form a solid polymer scaffold from the first component and also advancing the carrier away from the build surface to form a three-dimensional intermediate having the same shape as, or a shape to be imparted to, the three-dimensional object, and containing the second solidifiable component carried in the scaffold in unsolidified and/or uncured form; and (d) concurrently with or subsequent to the irradiating step, solidifying and/or curing the second solidifiable component in the three-dimensional intermediate to form the three-dimensional object.

A method of forming a three-dimensional object is carried out by: (a) providing a carrier and an optically transparent member having a build surface, the carrier and the build surface defining a build region therebetween; (b) filling the build region with a polymerizable liquid, the polymerizable liquid including a mixture of (i) a light polymerizable liquid first component, and (ii) a second solidifiable component that is different from the first component; (c) irradiating the build region with light through the optically transparent member to form a solid polymer scaffold from the first component and also advancing the carrier away from the build surface to form a three-dimensional intermediate having the same shape as, or a shape to be imparted to, the three-dimensional object, and containing the second solidifiable component carried in the scaffold in unsolidified and/or uncured form; and (d) concurrently with or subsequent to the irradiating step, solidifying and/or curing the second solidifiable component in the three-dimensional intermediate to form the three-dimensional object.

A polymerizable liquid, or resin, useful for the production by additive manufacturing of a three-dimensional object of polyurethane, polyurea, or a copolymer thereof, is described. The resin includes at least one of (i) a blocked or reactive blocked prepolymer, (ii) a blocked or reactive blocked diisocyanate, or (iii) a blocked or reactive blocked diisocyanate chain extender.

A method of forming a three-dimensional object is carried out by: (a) providing a carrier and an optically transparent member having a build surface, the carrier and the build surface defining a build region therebetween; (b) filling the build region with a polymerizable liquid, the polymerizable liquid comprising a mixture of (i) a light polymerizable liquid first component, and (ii) a second solidifiable component that is different from the first component; and (c) irradiating the build region with light through the optically transparent member to form a solid polymer scaffold from the first component and also advancing the carrier away from the build surface to form a three-dimensional intermediate having the same shape as, or a shape to be imparted to, the three-dimensional object and containing the second solidifiable component carried in the scaffold in unsolidified and/or uncured form; then (d) supporting the three dimensional intermediate with a separate support media; then (e) solidifying and/or curing the second solidifiable component in the three-dimensional intermediate to form the three-dimensional object in the support media; and then (f) separating the support media from the three-dimensional object.

A polymerizable liquid, or resin, useful for the production by additive manufacturing of a three-dimensional object of polyurethane, polyurea, or a copolymer thereof, is described. The resin includes at least one of (i) a blocked or reactive blocked prepolymer, (ii) a blocked or reactive blocked diisocyanate, or (iii) a blocked or reactive blocked diisocyanate chain extender.

A method of making a polyimide (PI)-based material. In one embodiment, the method begins by dispersing a polyamic acid (PAA) oligomer and photo-initiator into a photo-reactive monomer to form a liquid resin. In contrast to the above-described prior art, the liquid resin is substantially devoid of any non-reactive solvents. Electromagnetic radiation is then applied (e.g., in a 3D printing operation) to solidify the liquid resin and to substantially form a interpenetrating polymer network (IPN) in which the PAA oligomer is entangled within the network formed by the photo-reactive monomer but remains substantially independent and un-crosslinked from the PAA oligomer. Thereafter, the PAA-based IPN is thermally cycled to form a polyimide-based IPN.

A method of forming the body portion of a three-dimensional object from a polymerizable liquid by the process of continuous liquid interface printing is described. The body portion has a plurality of contiguous segments, and the process includes advancing a carrier for the object away from a build surface while irradiating a build region between the carrier and build surface in a pattern of advancing and irradiating defined by an operating mode. In the present invention, the operating mode is changed at least once during the formation of the body portion for different contiguous segments of the body portion.

A method of forming a three-dimensional object is described. The method may use a polymerizable liquid, or resin, useful for the production by additive manufacturing of a three-dimensional object, comprising a mixture of (i) a light polymerizable liquid first component, and (ii) a second solidifiable component that is different from said first component.