METHODS OF MANUFACTURING POLYMER DERIVED CERAMIC PARTICLES.
Methods for forming small volumetric shapes of polymer derived ceramic materials, including liquid-liquid forming methods, tower forming methods, and methods using high intensity electromagnetic radiation to cure the liquid to a cured preform material. Systems and apparatus for forming small volumetric shapes of polymer derived ceramic materials, cured materials and pyrolized materials, including liquid-liquid forming methods, tower forming methods, and methods using high intensity electromagnetic radiation to cure thin films of liquid polymer derived ceramic materials. Polysilocarb polymer derived ceramic precursor formulations.
1 . A system for making small volumetric structures from a polymer derived ceramic precursor, the system comprising:
a. a polymer derived ceramic precursor delivery apparatus, the apparatus comprising a chamber in fluid communication with a delivery port; wherein the chamber is capable of delivering a liquid polymer derived ceramic precursor;
b. a forming apparatus, the forming apparatus comprising a forming chamber having an opening; the chamber defining a cavity; wherein the cavity is in fluid communication with the chamber opening;
c. the chamber opening in fluid communication with the delivery port; whereby the system is capable of delivering the liquid polymer derived ceramic from the delivery port to the cavity as a liquid;
d. a temperature control apparatus thermally associated with the forming apparatus; wherein the cavity is capable of being maintained at a predetermined temperature; and,
e. whereby, the system is capable of providing a liquid polymer derived ceramic precursor to the cavity in a predetermined volumetric shape; and wherein the system is capable of curing the polymer derived ceramic precursor in the cavity.
2 . The system of claim 1 , wherein the delivery apparatus comprises a nozzle.
3 . The system of claim 1 , wherein the delivery apparatus comprises a pressure-driven droplet forming device
4 . The system of claim 1 , wherein the delivery apparatus comprises a flow driven droplet forming device.
5 . The system of claim 1 , wherein the delivery apparatus comprises an acoustic droplet ejection device.
6 . The system of claim 1 , wherein the forming apparatus comprises a shear induced droplet creation device.
7 . The system of claim 1 , wherein the delivery apparatus comprises a droplet creation device.
8 . The system of claim 1 , wherein the delivery apparatus comprises a droplet creation device; and the droplet creation device comprises an actuator; wherein the actuator is selected from the group consisting of piezo-electric, pressure reservoir, syringe, positive displacement, vibratory, electromagnetic, and phase change.
9 . The system of claim 1 , wherein the delivery apparatus comprises a droplet creation device selected from the group consisting of piezo-electric, pressure reservoir, syringe, positive displacement, vibratory, electromagnetic, and phase change.
10 . The system of claim 1 , wherein the forming apparatus comprises a droplet creation device.
11 . The system of claim 1 , wherein the forming apparatus comprises a droplet creation device; and the droplet creation device comprises an actuator; wherein the actuator is selected from the group consisting of piezo-electric, pressure reservoir, aerosol, syringe, positive displacement, vibratory, electromagnetic, and phase change.
12 . The system of claim 1 , wherein the forming apparatus comprises a droplet creation device selected from the group consisting of piezo-electric, pressure reservoir, syringe, aerosol, positive displacement, vibratory, electromagnetic, and phase change.
13 . The system of claim 1 , comprising a droplet creation device.
14 . The system of claim 1 , comprising a droplet creation device; and the droplet creation device comprises an actuator; wherein the actuator is selected from the group consisting of piezo-electric, pressure reservoir, syringe, positive displacement, aerosol, vibratory, electromagnetic, and phase change.
15 . The system of claim 1 , comprising a droplet creation device selected from the group consisting of piezo-electric, pressure reservoir, syringe, positive displacement, aerosol, vibratory, electromagnetic, and phase change.
16 . The system of claim 1 , comprising a droplet creation device selected from the group consisting of water-atomizer, gas-blast atomizer, atomizer, gas-assist atomizer, ultrasonic nebulizer, ultrasonic extruder, inkjet, and fogger.
17 . The system of claim 1 , wherein the port is configured to deliver a volumetric shape of precursor having a volume of less than about 0.25 inch 3 .
18 . The system of claim 2 , wherein the port is configured to deliver a volumetric shape of precursor having a volume of less than about 500 mm 3 .
19 . The system of claim 3 , wherein the port is configured to deliver a volumetric shape of precursor having a volume of less than about 100 mm 3 .
20 . The system of claim 15 wherein, the port is configured to deliver a volumetric shape of precursor having a volume of less than about 4,000 microns 3 .
21 . The system of claim 1 , wherein the port is configured to deliver a volumetric shape of precursor having a volume of less than about 50 microns 3 .
22 . The system of claim 1 , wherein the delivery apparatus is configured to deliver a volumetric shape of precursor having a volume of less than about 0.25 inch 3 .
23 . The system of claim 1 , wherein the delivery apparatus is configured to deliver a volumetric shape of precursor having a volume of less than about 100 mm 3 .
24 . The system of claim 10 , wherein the delivery apparatus is configured to deliver a volumetric shape of precursor having a volume of less than about 50 microns 3 .
25 . The system of claim 1 , wherein the delivery apparatus is configured to deliver a volumetric shape of precursor having a volume of less than about 10 microns 3 .
26 . The system of claim 1 , wherein the forming apparatus is configured to cure a volumetric shape of precursor having a volume of less than about 0.25 inch 3 .
27 . The system of claim 1 , wherein the forming apparatus is configured to cure a volumetric shape of precursor having a volume of less than about 4,000 microns 3 .
28 . The system of claim 1 , wherein the forming apparatus comprises a forming liquid.
29 . The system of claim 1 , wherein the forming apparatus comprises a forming liquid consisting essentially of water and a surfactant.
30 . The system of claim 1 , wherein the forming apparatus comprises a forming liquid and a mixer.
31 . The system of claim 1 , wherein the temperature control apparatus comprises a controller for providing a predetermined temperature profile.
32 . The system of claim 1 , wherein the temperature control apparatus comprises a controller for providing a predetermined temperature profile, the temperature profile comprising a first heating rate, a first hold time, a second heating rate and a second hold time.
33 . The system of claim 28 , wherein the temperature control apparatus comprises a controller for providing a predetermined temperature profile, the temperature profile comprising a first heating rate, a first hold time, a second heating rate and a second hold time.
34 . A system for making volumetric structures from a polymer derived ceramic precursor, the system comprising:
a. a polymer derived ceramic delivery apparatus, the apparatus comprising a liquid polymer derived ceramic precursor, a chamber and a port, wherein the chamber is capable of holding a liquid polymer derived ceramic precursor for delivery by the port into a volumetric shape having a predetermined volume;
b. a precursor solidifying apparatus, the solidifying apparatus comprising: a cavity; a temperature control apparatus; wherein the cavity is maintained at a predetermined temperature sufficient to cure the volumetric shape of polymer derived ceramic precursor to form a preform; and
c. the port in fluid communication with the cavity;
d. whereby, the system is capable of forming and curing the liquid polymer derived ceramic precursor into a predetermined volumetric shape structure.
35 . The system of claim 34 , comprising a droplet creation device selected from the group consisting of piezo-electric, pressure reservoir, syringe, aerosol, positive displacement, vibratory, electromagnetic, and phase change.
36 . The system of claim 34 , wherein the chamber is a tube.
37 . The system of claim 34 , wherein the port is a nozzle.
38 . The system of claim 34 , wherein the port is located inside of the cavity.
39 . The system of claim 34 , wherein the cavity contains a forming liquid.
40 . The system of claim 34 , wherein the cavity contains a forming liquid, having a surface; and the port is located below the surface.
41 . The system of claim 34 , wherein the volumetric shape is a shape selected from the group consisting of spheres, pellets, rings, lenses, and disks.
42 . The system of claim 34 , wherein the volumetric shape is a shape selected from the group consisting of channels, hollow sealed chambers, hollow spheres, blocks, sheets, and coatings.
43 . The system of claim 34 , configured to provide preforms having a predetermined size and to provide at least about 90% of the preforms at the predetermined size.
44 . The system of claim 34 , configured to provide preforms having a predetermined size and to provide at least about 95% of the preforms at the predetermined size.
45 . The system of claim 34 , configured to provide preforms having a predetermined size and to provide at least about 99% of the preforms at the predetermined size.
46 . The system of claim 34 , wherein the volumetric shape of precursor has a volume of less than about 0.25 inch 3 .
47 . The system of claim 34 , wherein the volumetric shape of precursor has a volume of less than about 500 mm 3 .
48 . The system of claim 39 , wherein the volumetric shape of precursor has a volume of less than about 100 mm 3 .
49 . The system of claim 39 , wherein the volumetric shape of precursor has a volume of less than about 4,000 microns 3 .
50 . The system of claim 39 , wherein the volumetric shape of precursor has a volume of less than about 10 microns 3 .
51 . The system of claim 1 , wherein the system comprises an extruder; wherein the delivery apparatus and the forming apparatus are components of the extruder.
52 . The system of claim 34 , wherein the system comprises an extruder; wherein the delivery apparatus and the solidifying apparatus are components of the extruder.
53 . A system for making volumetric structures from a polymer derived ceramic precursor material, the system comprising:
a. a polymer derived ceramic delivery apparatus, the apparatus comprising a first chamber in fluid communication with a delivery port, and an amount of a liquid polymer derived ceramic precursor;
b. a forming and curing apparatus, the forming and curing apparatus comprising a forming chamber having an opening; and the chamber defining a cavity, wherein the cavity is in fluid communication with the chamber opening and contains a volumetric shape of a polymer derived ceramic precursor;
c. the chamber opening in fluid communication with the delivery port;
d. a temperature control source thermally associated with the forming apparatus; wherein the cavity is maintained at a predetermined temperature sufficient to cure the volumetric shape of the polymer derived ceramic precursor; and,
e. whereby, the system is capable of providing a liquid polymer derived ceramic precursor material into the cavity in a predetermined volumetric shape, and wherein the polymer derived ceramic precursor material is cured in the cavity.
54 . The system of claim 53 , wherein the liquid polymer derived ceramic precursor is selected from the group consisting of silanes, polysilanes, silazanes, polysilazanes, carbosilanes, polycarbosilanes, siloxanes, and polysiloxanes.
55 . The system of claim 53 , wherein the liquid polymer derived ceramic precursor is a polysilocarb.
56 . The system of claim 53 , wherein the liquid polymer derived ceramic precursor is a net polysilocarb.
57 . The system of claim 53 , wherein the liquid polymer derived ceramic precursor is a reinforced polysilocarb.
58 . The system of claim 53 , wherein the liquid polymer derived ceramic precursor comprises a polysilocarb and contains hydride groups.
59 . The system of claim 53 , wherein the liquid polymer derived ceramic precursor comprises a polysilocarb, is solvent free, and contains hydride groups.
60 . The system of claim 53 , wherein the liquid polymer derived ceramic precursor comprises a polysilocarb and contains vinyl groups.
61 . The system of claim 53 , wherein the liquid polymer derived ceramic precursor comprises a polysilocarb having hydride and vinyl groups and wherein the molar ratio of hydride groups to vinyl groups is about 1.50 to 1.
62 . The system of claim 53 , wherein the liquid polymer derived ceramic precursor comprises a polysilocarb having hydride and vinyl groups and wherein the molar ratio of hydride groups to vinyl groups is about 3.93 to 1.
63 . The method of claim 53 , wherein the liquid polymer derived ceramic precursor comprises a polysilocarb having hydride and vinyl groups and wherein the molar ratio of hydride groups to vinyl groups is about 1.75 to 1 to about 23.02 to 1.
64 . A system for making small volumetric structures from a polymer derived ceramic precursor material, the system comprising:
a. a polymer derived ceramic delivery apparatus, the apparatus comprising a first chamber in fluid communication with a delivery port, and an amount of a liquid polymer derived ceramic precursor;
b. a forming apparatus, the forming apparatus comprising a chamber having an opening; and the chamber defining a cavity, wherein the cavity is in fluid communication with the chamber opening and contains a volumetric shape of a polymer derived ceramic precursor;
c. the chamber opening in fluid communication with the delivery port; and,
d. whereby, the system is capable of providing a liquid polymer derived ceramic precursor into the cavity.
65 . The system of claim 64 , wherein the liquid polymer derived ceramic precursor is selected from the group consisting of silanes, polysilanes, silazanes, polysilazanes, carbosilanes, polycarbosilanes, silazanes, polysilazanes, siloxanes, and polysiloxanes.
66 . The system of claim 64 , wherein the liquid polymer derived ceramic precursor is a polysilocarb.
67 . The system of claims 66 , wherein the volume is less than about 0.25 inch 3 .
68 . The system of claims 66 , wherein the volume is less than about 500 mm 3 .
69 . The system of claims 66 , wherein the volume is than about 50 microns 3 .
70 . A system for making small volumetric structures from a polymer derived ceramic precursor, the system comprising:
a. a means for delivering a liquid polymer derived ceramic;
b. a forming apparatus, the forming apparatus comprising a forming chamber having an opening; and the chamber defining a cavity, wherein the cavity is in fluid communication with the chamber opening;
c. the chamber opening in fluid communication with the delivery means, whereby the delivery means is capable of delivering the liquid polymer derived ceramic into the cavity; and,
d. a temperature control source thermally associated with the forming apparatus, wherein the cavity is maintained at a predetermined temperature;
e. whereby, the system is capable of providing a liquid polymer derived ceramic precursor material into the cavity in a predetermined shape, and fixing the polymer derived ceramic in the predetermined shape; thereby making a volumetrically shaped polymer derived ceramic preform.
71 . A system for making small volumetric structures from a polymer derived ceramic precursor, the system comprising:
a. a polymer derived ceramic delivery apparatus, the apparatus comprising a first chamber in fluid communication with a delivery port; wherein the first chamber is capable of holding a liquid polymer derived ceramic precursor;
b. a means for forming a volumetric shaped structure, the forming means comprising a forming chamber having an opening; and the chamber defining a cavity, wherein the cavity is in fluid communication with the chamber opening;
c. the chamber opening in fluid communication with the delivery port, whereby the system is capable of delivering the liquid polymer derived ceramic from the delivery port into the cavity, as a liquid;
d. a temperature control source thermally associated with the forming apparatus, wherein the cavity is maintained at a predetermined temperature; and,
e. whereby, the system is capable of providing a liquid polymer derived ceramic precursor material into the cavity in a predetermined volumetric shape, and wherein the polymer derived ceramic precursor material is cured in the cavity.
72 . A system for making small volumetric structures from a polymer derived ceramic precursor, the system comprising:
a. a means for delivering a liquid polymer derived ceramic;
b. a means for forming a volumetric shaped structure, the forming means comprising a forming chamber having an opening; and the chamber defining a cavity, wherein the cavity is in fluid communication with the chamber opening;
c. the chamber opening in fluid communication with the delivery port, whereby the system is capable of delivering the liquid polymer derived ceramic from the delivery port into the cavity, as a liquid;
d. a temperature control source thermally associated with the forming apparatus, wherein the cavity is maintained at a predetermined temperature; and,
e. whereby, the system is capable of providing a liquid polymer derived ceramic precursor material into the cavity in a predetermined volumetric shape, and wherein the polymer derived ceramic precursor material is cured in the cavity.
73 . A system for making small volumetric structures from a polymer derived ceramic precursor, the system comprising:
a. a means for forming a small volumetric shaped structure of polymer derived ceramic precursor; and,
b. a means for curing the small volumetric shaped structure of polymer derived ceramic precursor material into a volumetric shaped preform.
74 . A system for making small volumetric structures from a polymer derived ceramic precursor, the system comprising:
a. a means for forming a small volumetric shaped structure of polymer derived ceramic precursor;
b. a means for curing the small volumetric shaped structure of polymer derived ceramic precursor material into a volumetric shaped preform; and,
c. a means for pyrolizing the preform.
75 . A system for making small volumetric structures from a polymer derived ceramic precursor, the system comprising:
a. a liquid holding receptacle;
b. the liquid holding receptacle containing a forming liquid;
c. a precursor delivery apparatus, comprising a precursor, a channel, and a delivery port, the channel in fluid communication with the delivery port, whereby the precursor can be delivered from the delivery port; and,
d. the delivery port in fluid communication with the liquid holding receptacle.
76 . A method for making small volumetric structures from a polymer derived ceramic precursor, the method comprising:
a. providing a liquid polymer derived ceramic precursor to a delivery apparatus, the apparatus comprising a chamber in fluid communication with a delivery port;
b. forming the liquid precursor into a predetermined liquid volumetric shape; and delivering the liquid volumetric shape to a chamber defining a cavity; and,
c. curing the liquid volumetric shape in the cavity to form a polymer derived ceramic preform.
77 . The method of claim 76 , wherein the preform is the same shape as the volumetric shape.
78 . The method of claim 76 , wherein the preform is substantially the same shape as the volumetric shape.
79 . The method of claim 76 , wherein the preform is green cured.
80 . The method of claim 76 , wherein the preform is hard cured.
81 . The method of claim 76 , wherein the preform is final cured.
82 . The method of claim 76 , comprising pyrolizing the preform to form a polymer derived ceramic.
83 . The method of claim 76 , wherein the delivery apparatus comprises a nozzle.
84 . The method of claim 76 , wherein in the forming of the volumetric shape comprising particle creation selected from the group of forming processes consisting of piezo-electric, pressure reservoir, syringe, positive displacement, aerosol, vibratory, electromagnetic, and phase change.
85 . The methods of claim 76 , wherein, the volumetric shape of precursor has a volume of less than about 0.25 inch 3 .
86 . The methods of claim 76 , wherein, the volumetric shape of precursor has a volume of less than about 50 microns 3 .
87 . The methods of claim 76 , wherein, the volumetric shape of precursor has a volume of less than about 10 microns 3 .
88 . The method of claim 76 , wherein the cavity comprises a forming liquid.
89 . The method of claim 76 , wherein the cavity comprises a forming liquid consisting essentially of water and a surfactant.
90 . The method of claim 76 , wherein the cavity comprises a forming liquid and a mixer.
91 . The method of claim 76 , wherein the cavity is an extruder cavity.
92 . The method of claim 76 , wherein the cure is conducted with a predetermined cure temperature profile.
93 . The method of claim 76 , wherein the cure is conducted with a predetermined cure temperature profile comprising a first heating rate, a first hold time, a second heating rate and a second hold time.
94 . The method of claim 76 , wherein the volumetric shape is a shape selected from the group consisting of spheres, pellets, rings, lenses, and disks.
95 . The method of claim 76 , wherein at least about 90% of the preforms are a predetermined size.
96 . The method of claim 76 , wherein at least about 95% of the preforms are a predetermined size.
97 . The method of claim 76 , wherein at least about 99% of the preforms are a predetermined size.
98 . The method of claim 76 , wherein the liquid polymer derived ceramic precursor is a polysilocarb.
99 . The method of claim 76 , wherein the liquid polymer derived ceramic precursor is a net polysilocarb.
100 . The method of claim 76 , wherein the liquid polymer derived ceramic precursor is a reinforced polysilocarb.
101 . The method of claim 76 , wherein the liquid polymer derived ceramic precursor comprises a polysilocarb and contains hydride groups.
102 . The method of claim 76 , wherein the liquid polymer derived ceramic precursor comprises a polysilocarb, is solvent free, and contains hydride groups.
103 . The method of claim 76 , wherein the liquid polymer derived ceramic precursor comprises a polysilocarb and contains vinyl groups.
104 . The method of claim 76 , wherein the liquid polymer derived ceramic precursor comprises a polysilocarb, is solvent free, and contains vinyl groups.
105 . The method of claim 76 , wherein the liquid polymer derived ceramic precursor comprises a polysilocarb having hydride and vinyl groups and wherein the molar ratio of hydride groups to vinyl groups is about 1.50 to 1.
106 . The method of claim 76 , wherein the liquid polymer derived ceramic precursor comprises a polysilocarb having hydride and vinyl groups and wherein the molar ratio of hydride groups to vinyl groups is about 3.93 to 1.
107 . The method of claim 76 , wherein the liquid polymer derived ceramic precursor comprises a polysilocarb having hydride and vinyl groups and wherein the molar ratio of hydride groups to vinyl groups is about 0.08 to 1 to about 1.82 to 1.
108 . The method of claim 76 , wherein the molar ratio of hydride groups to vinyl groups is about 1.12 to 1 to about 2.36 to 1.
109 . The method of claim 76 , wherein the molar ratio of hydride groups to vinyl groups is about 1.75 to 1 to about 23.02 to 1.
110 . A method for making small volumetric structures from a polymer derived ceramic precursor, the system comprising:
a. a step for forming a liquid polymer derived ceramic to a liquid predetermined volumetric shape; and,
b. a step for curing the liquid predetermined volumetric shape into a preform having essentially the same volumetric shape.
111 . A method for making small volumetric structures from a polymer derived ceramic precursor, the system comprising:
a. a step for forming a small volumetric shaped structure of polymer derived ceramic precursor;
b. a step for curing the small volumetric shaped structure of polymer derived ceramic precursor material into a volumetric shaped preform; and,
c. a step for pyrolizing the preform.
112 . A method for making small volumetric structures from a polymer derived ceramic precursor, the system comprising:
a. forming a net small volumetric shaped structure of polymer derived ceramic precursor;
b. curing the net small volumetric shaped structure of polymer derived ceramic precursor material into a volumetric shaped preform; and,
c. pyrolizing the preform.
113 . A method for making small volumetric structures from a polymer derived ceramic precursor, the system comprising:
a. providing a polymer derived ceramic precursor to a liquid holding receptacle;
b. the liquid holding receptacle containing a forming liquid;
c. the precursor forming essentially upon contact with the forming liquid a predetermined volumetric shape; and,
d. curing the volumetric shape to form a preform.
114 . The method of claim 113 , wherein the volumetric shape is a bead.
115 . The method of claim 113 , comprising pyrolizing the preform.
116 . The method of claim 113 , wherein the volumetric shape is a sphere and comprising pyrolizing the sphere.
117 . A system for forming polymer derived ceramic platelets, the system comprising:
a. a means for forming a thin film of liquid polymer derived ceramic precursor material on a substrate means; and,
b. a means for providing electromagnetic radiation to the thin film of liquid polymer derived ceramic;
118 . The system of claim 117 , wherein the means for forming the thin film is a distribution header.
119 . The system of claim 117 , wherein the means for forming the thin film is a distribution roller assembly.
120 . The system of claim 117 , wherein the means for forming the thin film is an air knife assembly.
121 . The system of claim 117 , wherein the electromagnetic radiation is white light.
122 . The system of claim 117 , wherein the electromagnetic radiation is broad band light, having a wavelength band of at least about 100 nm, between the wavelengths of about 300 nm and about 800 nm.
123 . A method of forming a cured polymer derived ceramic from a liquid polymer derived ceramic precursors, the method comprising:
a. a step for forming a thin layer of a liquid polymer derived ceramic precursor on a substrate; and,
b. a step for curing the thin layer with electromagnetic radiation.