Patent · US10087556B2 · B2 · US

Reduced density article

(11) Publication number

US10087556B2

(21) Application number

15/036,562

(22) Filing date

2014-11-07

(30) Priority date

2013-11-21

(43) Publication date

2018-10-02

(45) Date of grant

2018-10-02

(51) IPC

B29C 67/00; B33Y 10/00; B33Y 70/00; B33Y 80/00; C08K 5/523; C08K 5/526; C09D 169/00; D01F 1/10; D01F 6/64; B29C 64/106

(52) CPC

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: 64/118, 64/106
B22F Working metallic powder; manufacture of articles from metallic powder; making metallic powder; apparatus or devices specially adapted for metallic powder: 10/18, 10/32
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: 2069/00
B33Y 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: 10/00, 70/00, 70/10, 80/00
C08K Use of inorganic or non-macromolecular organic substances as compounding ingredients: 5/523, 5/526
C08L Compositions of macromolecular compounds: 69/00
C09D Coating compositions, e.g. paints, varnishes or lacquers; filling pastes; chemical paint or ink removers; inks; correcting fluids; woodstains; pastes or solids for colouring or printing; use of materials therefor: 169/00
D01F Chemical features in the manufacture of artificial filaments, threads, fibres, bristles or ribbons; apparatus specially adapted for the manufacture of carbon filaments: 1/10, 6/64
D10B Indexing scheme associated with sublasses of section d, relating to textiles: 2401/041
Y02P Climate change mitigation technologies in the production or processing of goods: 10/25

(73) Assignee

SABIC Global Technologies BV

(72) Inventors

Robert R. Gallucci; Vandita Pai-Paranjape; Thomas Hocker; Keith E. Cox

(54) Title

Reduced density article

(57) Abstract

A reduced density article of manufacture, and process for making same, made from a thermoplastic polycarbonate composition. The reduced density article of manufacture has (1) a certain density and (2) a certain micro structure containing from 1% to 20% by volume of voids wherein at least 80% of the voids are high aspect voids and less than 20% of the voids are spherical voids with a diameter of 10 to 100 microns. The polycarbonate thermoplastic composition comprises at least 50 mole % of a certain bisphenol A. The reduced density article of manufacture is made by a monofilament additive manufacturing technique.

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Claims (20)

A reduced density article of manufacture comprising a thermoplastic polycarbonate composition, the reduced density article of manufacture having (1) a density as measured by ASTM D792-00 of 80% to 99% by weight of a similar solid standard injection molded article having no voids and (2) a micro structure measured by optical microscopy containing from 1% to 20% by volume of voids wherein at least 80% of the voids are high aspect voids and less than 20% of the voids are spherical voids with a diameter of 10 to 100 microns; wherein the polycarbonate thermoplastic composition comprises at least 50 mole % bisphenol A having a weight-average molecular weight (Mw) of 10,000 to 50,000, a glass transition temperature (Tg) from 130 to 180 degrees C., a phenolic OH end group content of less than 50 ppm, a halide group content below 100 ppm, and a diaryl carbonate content below 1% by weight; and wherein the reduced density article of manufacture is made by a monofilament additive manufacturing technique.
The reduced density article of manufacture of claim 1 wherein the reduced density article of manufacture further comprises at least 50 ppm of a triaryl phosphate having a weight average molecular weight (Mw) of at least 300.
The reduced density article of manufacture of claim 1 wherein the reduced density article of manufacture further comprises at least 100 ppm of a mixture of triaryl phosphate and triaryl phosphite each having a weight average molecular weight (Mw) of at least 300, wherein the wherein the triaryl phosphate is present in a greater amount than the triaryl phosphite.
The reduced density article of manufacture of claim 1 wherein thermoplastic polycarbonate composition has a carbamate group content of less than 10 ppm.
The reduced density article of manufacture of claim 1 wherein the article has high surface roughness with vertical deviation of at least 0.01 mm, or wherein the article has a grooved surface as measured by ISO 4287 (1997) with a groove depth from 20 to 100 micro meters (μm) and groove spacing of from 0.05 to 2.0 mm.
The reduced density article of manufacture of claim 1 wherein the reduced density article of manufacture further comprises a thermoplastic material chosen from acrylonitrile butadiene styrene (ABS), acrylic rubber, methacrylate styrene butadiene (MB S), polyacrylates (acrylic), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polycyclohexylene dimethylene terephthalate (PCT), polyhydroxyalkanoates (PHAs), polyester carbonates, polyetherimide (PEI), polytrimethylene terephthalate (PTT), styrene-acrylonitrile (SAN), silicone polycarbonate copolymers, or any combination thereof and, optionally, wherein the article comprises less than 5 weight % of a member selected from the group consisting of (i) polyvinyl chloride (PVC), polyvinylidene chloride, polyacetal, cellulosics; cellulose acetate, cellulose butyrate, cellulose propionate, polychloroprene, melamine formaldehyde, urea formaldehyde, polyacrylamide, and combinations thereof.
The reduced density article of manufacture of claim 1 wherein at least 90% of the voids are high aspect voids and less than 10% of the voids are spherical voids with a diameter of 10 to 100 microns.
The reduced density article of manufacture of claim 1 wherein least 20% of the voids are angular voids having a cusp angle that is an acute angle of 60 degrees or less.
The reduced density article of manufacture of claim 1 wherein the article has a tensile strength at yield of greater than 5,000 psi, and a flex modulus at 100° C. greater than 1,000 psi.
The article of claim 1 wherein the reduced density article of manufacture further comprises a colorant chosen from solvent violet 36, pigment blue 60, pigment blue 15:1, pigment blue 15.4, carbon black, titanium dioxide or any combination thereof.
The article of claim 1 wherein the high aspect voids have an aspect ratio from 2:1 to 100:1 with a major length of less than 5 mm.
A reduced density article of manufacture comprising a mixture of thermoplastic polycarbonate composition and at least 50 ppm of a triaryl phosphate having a weight average molecular weight (Mw) of at least 300, the reduced density article of manufacture having (1) a density as measured by ASTM D792-00 of 80% to 95% by weight of a similar standard injection molded article having no voids; (2) having a micro structure as measured by optical microscopy containing from 1% to 20% by volume of voids wherein at least 80% of the voids are high aspect voids have an aspect ratio from 2:1 to 100:1 with a major length of less than 5 mm and less than 20% of the voids are spherical voids with a diameter of 10 to 100 microns; wherein the polycarbonate thermoplastic composition comprises at least 50 mole % bisphenol A having a weight-average molecular weight (Mw) of 10,000 to 50,000, a glass transition temperature (Tg) from 130 to 180 degrees C., a phenolic OH end group content of less than 50 ppm, a halide group content below 100 ppm, and a diaryl carbonate content below 1% by weight, a tensile strength at yield of greater than 5,000 psi, and a flex modulus at 100° C. greater than 1,000 psi; and wherein the reduced density article of manufacture is made by an monofilament additive manufacturing technique using a monofilament having a diameter from 0.01 to 5.0 mm.
The reduced density article of manufacture of claim 12 wherein the material in the article contains at least 100 ppm of a mixture of triaryl phosphate and triaryl phosphite each having a weight average molecular weight (Mw) of at least 300, wherein the wherein the triaryl phosphate is present in a greater amount than the triaryl phosphite.
A process for making a reduced density article of manufacture comprising (1) depositing a multitude of thermoplastic monofilament strands having a diameter from 0.1 to 20.0 mm using a fused deposition modeling apparatus in a crossing pattern and (2) fusing the multitude of strands together to make a reduced density article of manufacture having voids therein; wherein the a reduced density article of manufacture comprises a thermoplastic polycarbonate composition, the reduced density article of manufacture having (a) a density as measured by ASTM D792-01 of 80% to 99% by weight of a similar standard injection molded article having no voids and (b) a micro structure as measured by optical microscopy containing from 1% to 20% by volume of voids wherein at least 80% of the voids are high aspect voids and less than 20% of the voids are spherical voids with a diameter of 10 to 100 microns; wherein the polycarbonate thermoplastic composition comprises at least 50 mole % bisphenol A having a weight-average molecular weight (Mw) of 10,000 to 50,000, a glass transition temperature (Tg) from 130 to 180 degrees C., a phenolic OH end group content of less than 50 ppm, a halide group content below 100 ppm, and a diaryl carbonate content below 1% by weight.
The process for making a reduced density article of manufacture of claim 14 wherein steps (1) and (2) are carried out in an inert atmosphere containing less than 1 volume % oxygen and wherein the inert atmosphere is chosen from nitrogen, carbon dioxide, argon, krypton, xenon and mixtures thereof.
The process for making a reduced density article of manufacture of claim 14 wherein each monofilament comprises a thermoplastic polycarbonate composition strand with a diameter of 0.1 to 5 mm that is deposited by an extrusion head of a fused deposition modeling apparatus in an oven at a temperature from 280 to 380 degrees C. for average residence time from 30 to 300 minutes, wherein the thermoplastic polycarbonate composition has a change of weight average molecular weight (Mw) of less than 15% of the original molecular weight.
The process for making a reduced density article of manufacture of claim 14 wherein reduced density article of manufacture further comprises at least 50 ppm of a mixture of triaryl phosphate and triaryl phosphite each having a weight average molecular weight (Mw) of at least 300, wherein the triaryl phosphate is present in a greater amount than the triaryl phosphite.
The process for making a reduced density article of manufacture of claim 14 wherein the multitude of thermoplastic monofilaments are not dried before fusing.
The process for making a reduced density article of manufacture of claim 14 wherein the majority of the major lengths of the high aspect voids are oriented in the direction of strand length.
A reduced density article of claim 1 comprising a tube, duct, hose, pipe, connector, conduit, enclosure for electrical equipment, parts of motors, compressors, exhaust manifolds, mufflers, parts of heating and air conditioning systems, kettles, carafes, bottles, jars, reservoirs, fuel or oil tanks, power distribution equipment, communication devices, personal grooming devices, toys and sculptures.

Description

Additive Manufacturing (AM) is a new production technology that is transforming the way all sorts of things are made. AM makes three-dimensional (3D) solid objects of virtually any shape from a digital model. Generally, this is achieved by creating a digital blueprint of a desired solid object with computer-aided design (CAD) modeling software and then slicing that virtual blueprint into very small digital cross-sections. These cross-sections are formed or deposited in a sequential layering process in an AM machine to create the 3D object. AM has many advantages, including dramatically reducing the time from design to prototyping to commercial product. Running design changes are possible. Multiple parts can be built in a single assembly. No tooling is required. Minimal energy is needed to make these 3D solid objects. It also decreases the amount waste and raw materials. AM also facilitates production of extremely complex geometrical parts. AM also reduces the parts inventory for a business since parts can be quickly made on-demand and on-site. However, AM has the disadvantages of slow cycle time and that that the cost of the materials used for each build are considerably higher than conventional injection molding operations. Thus, there is a need to lower the cost of those AM materials without sacrificing the process benefits and flexibility of the AM process.

Citations (43)

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US2999835A
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US20130071599A1
US20130224461A1
US20130261202A1
WO2015134316A1

Record as JSON

{
  "publication_number": "US10087556B2",
  "country": "US",
  "kind": "B2",
  "title": "Reduced density article",
  "abstract": "A reduced density article of manufacture, and process for making same, made from a thermoplastic polycarbonate composition. The reduced density article of manufacture has (1) a certain density and (2) a certain micro structure containing from 1% to 20% by volume of voids wherein at least 80% of the voids are high aspect voids and less than 20% of the voids are spherical voids with a diameter of 10 to 100 microns. The polycarbonate thermoplastic composition comprises at least 50 mole % of a certain bisphenol A. The reduced density article of manufacture is made by a monofilament additive manufacturing technique.",
  "claims": [
    "1. A reduced density article of manufacture comprising a thermoplastic polycarbonate composition, the reduced density article of manufacture having (1) a density as measured by ASTM D792-00 of 80% to 99% by weight of a similar solid standard injection molded article having no voids and (2) a micro structure measured by optical microscopy containing from 1% to 20% by volume of voids wherein at least 80% of the voids are high aspect voids and less than 20% of the voids are spherical voids with a diameter of 10 to 100 microns; wherein the polycarbonate thermoplastic composition comprises at least 50 mole % bisphenol A having a weight-average molecular weight (Mw) of 10,000 to 50,000, a glass transition temperature (Tg) from 130 to 180 degrees C., a phenolic OH end group content of less than 50 ppm, a halide group content below 100 ppm, and a diaryl carbonate content below 1% by weight; and wherein the reduced density article of manufacture is made by a monofilament additive manufacturing technique.",
    "2. The reduced density article of manufacture of claim 1 wherein the reduced density article of manufacture further comprises at least 50 ppm of a triaryl phosphate having a weight average molecular weight (Mw) of at least 300.",
    "3. The reduced density article of manufacture of claim 1 wherein the reduced density article of manufacture further comprises at least 100 ppm of a mixture of triaryl phosphate and triaryl phosphite each having a weight average molecular weight (Mw) of at least 300, wherein the wherein the triaryl phosphate is present in a greater amount than the triaryl phosphite.",
    "4. The reduced density article of manufacture of claim 1 wherein thermoplastic polycarbonate composition has a carbamate group content of less than 10 ppm.",
    "5. The reduced density article of manufacture of claim 1 wherein the article has high surface roughness with vertical deviation of at least 0.01 mm, or wherein the article has a grooved surface as measured by ISO 4287 (1997) with a groove depth from 20 to 100 micro meters (μm) and groove spacing of from 0.05 to 2.0 mm.",
    "6. The reduced density article of manufacture of claim 1 wherein the reduced density article of manufacture further comprises a thermoplastic material chosen from acrylonitrile butadiene styrene (ABS), acrylic rubber, methacrylate styrene butadiene (MB S), polyacrylates (acrylic), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polycyclohexylene dimethylene terephthalate (PCT), polyhydroxyalkanoates (PHAs), polyester carbonates, polyetherimide (PEI), polytrimethylene terephthalate (PTT), styrene-acrylonitrile (SAN), silicone polycarbonate copolymers, or any combination thereof and, optionally, wherein the article comprises less than 5 weight % of a member selected from the group consisting of (i) polyvinyl chloride (PVC), polyvinylidene chloride, polyacetal, cellulosics; cellulose acetate, cellulose butyrate, cellulose propionate, polychloroprene, melamine formaldehyde, urea formaldehyde, polyacrylamide, and combinations thereof.",
    "7. The reduced density article of manufacture of claim 1 wherein at least 90% of the voids are high aspect voids and less than 10% of the voids are spherical voids with a diameter of 10 to 100 microns.",
    "8. The reduced density article of manufacture of claim 1 wherein least 20% of the voids are angular voids having a cusp angle that is an acute angle of 60 degrees or less.",
    "9. The reduced density article of manufacture of claim 1 wherein the article has a tensile strength at yield of greater than 5,000 psi, and a flex modulus at 100° C. greater than 1,000 psi.",
    "10. The article of claim 1 wherein the reduced density article of manufacture further comprises a colorant chosen from solvent violet 36, pigment blue 60, pigment blue 15:1, pigment blue 15.4, carbon black, titanium dioxide or any combination thereof.",
    "11. The article of claim 1 wherein the high aspect voids have an aspect ratio from 2:1 to 100:1 with a major length of less than 5 mm.",
    "12. A reduced density article of manufacture comprising a mixture of thermoplastic polycarbonate composition and at least 50 ppm of a triaryl phosphate having a weight average molecular weight (Mw) of at least 300, the reduced density article of manufacture having (1) a density as measured by ASTM D792-00 of 80% to 95% by weight of a similar standard injection molded article having no voids; (2) having a micro structure as measured by optical microscopy containing from 1% to 20% by volume of voids wherein at least 80% of the voids are high aspect voids have an aspect ratio from 2:1 to 100:1 with a major length of less than 5 mm and less than 20% of the voids are spherical voids with a diameter of 10 to 100 microns; wherein the polycarbonate thermoplastic composition comprises at least 50 mole % bisphenol A having a weight-average molecular weight (Mw) of 10,000 to 50,000, a glass transition temperature (Tg) from 130 to 180 degrees C., a phenolic OH end group content of less than 50 ppm, a halide group content below 100 ppm, and a diaryl carbonate content below 1% by weight, a tensile strength at yield of greater than 5,000 psi, and a flex modulus at 100° C. greater than 1,000 psi; and wherein the reduced density article of manufacture is made by an monofilament additive manufacturing technique using a monofilament having a diameter from 0.01 to 5.0 mm.",
    "13. The reduced density article of manufacture of claim 12 wherein the material in the article contains at least 100 ppm of a mixture of triaryl phosphate and triaryl phosphite each having a weight average molecular weight (Mw) of at least 300, wherein the wherein the triaryl phosphate is present in a greater amount than the triaryl phosphite.",
    "14. A process for making a reduced density article of manufacture comprising (1) depositing a multitude of thermoplastic monofilament strands having a diameter from 0.1 to 20.0 mm using a fused deposition modeling apparatus in a crossing pattern and (2) fusing the multitude of strands together to make a reduced density article of manufacture having voids therein; wherein the a reduced density article of manufacture comprises a thermoplastic polycarbonate composition, the reduced density article of manufacture having (a) a density as measured by ASTM D792-01 of 80% to 99% by weight of a similar standard injection molded article having no voids and (b) a micro structure as measured by optical microscopy containing from 1% to 20% by volume of voids wherein at least 80% of the voids are high aspect voids and less than 20% of the voids are spherical voids with a diameter of 10 to 100 microns; wherein the polycarbonate thermoplastic composition comprises at least 50 mole % bisphenol A having a weight-average molecular weight (Mw) of 10,000 to 50,000, a glass transition temperature (Tg) from 130 to 180 degrees C., a phenolic OH end group content of less than 50 ppm, a halide group content below 100 ppm, and a diaryl carbonate content below 1% by weight.",
    "15. The process for making a reduced density article of manufacture of claim 14 wherein steps (1) and (2) are carried out in an inert atmosphere containing less than 1 volume % oxygen and wherein the inert atmosphere is chosen from nitrogen, carbon dioxide, argon, krypton, xenon and mixtures thereof.",
    "16. The process for making a reduced density article of manufacture of claim 14 wherein each monofilament comprises a thermoplastic polycarbonate composition strand with a diameter of 0.1 to 5 mm that is deposited by an extrusion head of a fused deposition modeling apparatus in an oven at a temperature from 280 to 380 degrees C. for average residence time from 30 to 300 minutes, wherein the thermoplastic polycarbonate composition has a change of weight average molecular weight (Mw) of less than 15% of the original molecular weight.",
    "17. The process for making a reduced density article of manufacture of claim 14 wherein reduced density article of manufacture further comprises at least 50 ppm of a mixture of triaryl phosphate and triaryl phosphite each having a weight average molecular weight (Mw) of at least 300, wherein the triaryl phosphate is present in a greater amount than the triaryl phosphite.",
    "18. The process for making a reduced density article of manufacture of claim 14 wherein the multitude of thermoplastic monofilaments are not dried before fusing.",
    "19. The process for making a reduced density article of manufacture of claim 14 wherein the majority of the major lengths of the high aspect voids are oriented in the direction of strand length.",
    "20. A reduced density article of claim 1 comprising a tube, duct, hose, pipe, connector, conduit, enclosure for electrical equipment, parts of motors, compressors, exhaust manifolds, mufflers, parts of heating and air conditioning systems, kettles, carafes, bottles, jars, reservoirs, fuel or oil tanks, power distribution equipment, communication devices, personal grooming devices, toys and sculptures."
  ],
  "description_excerpt": "Additive Manufacturing (AM) is a new production technology that is transforming the way all sorts of things are made. AM makes three-dimensional (3D) solid objects of virtually any shape from a digital model. Generally, this is achieved by creating a digital blueprint of a desired solid object with computer-aided design (CAD) modeling software and then slicing that virtual blueprint into very small digital cross-sections. These cross-sections are formed or deposited in a sequential layering process in an AM machine to create the 3D object. AM has many advantages, including dramatically reducing the time from design to prototyping to commercial product. Running design changes are possible. Multiple parts can be built in a single assembly. No tooling is required. Minimal energy is needed to make these 3D solid objects. It also decreases the amount waste and raw materials. AM also facilitates production of extremely complex geometrical parts. AM also reduces the parts inventory for a business since parts can be quickly made on-demand and on-site. However, AM has the disadvantages of slow cycle time and that that the cost of the materials used for each build are considerably higher than conventional injection molding operations. Thus, there is a need to lower the cost of those AM materials without sacrificing the process benefits and flexibility of the AM process.",
  "cpc": [
    "B29C 64/118",
    "B22F 10/18",
    "B22F 10/32",
    "B29C 64/106",
    "B29K 2069/00",
    "B33Y 10/00",
    "B33Y 70/00",
    "B33Y 70/10",
    "B33Y 80/00",
    "C08K 5/523",
    "C08K 5/526",
    "C08L 69/00",
    "C09D 169/00",
    "D01F 1/10",
    "D01F 6/64",
    "D10B 2401/041",
    "Y02P 10/25"
  ],
  "ipc": [
    "B29C 67/00",
    "B33Y 10/00",
    "B33Y 70/00",
    "B33Y 80/00",
    "C08K 5/523",
    "C08K 5/526",
    "C09D 169/00",
    "D01F 1/10",
    "D01F 6/64",
    "B29C 64/106"
  ],
  "assignees": [
    "SABIC Global Technologies BV"
  ],
  "inventors": [
    "Robert R. Gallucci",
    "Vandita Pai-Paranjape",
    "Thomas Hocker",
    "Keith E. Cox"
  ],
  "filing_date": "2014-11-07",
  "publication_date": "2018-10-02",
  "grant_date": "2018-10-02",
  "priority_date": "2013-11-21",
  "application_number": "US-201415036562-A",
  "family_id": "52014349",
  "cited_by_count": 115,
  "citations": [
    "US3153008A",
    "US2999835A",
    "US3334154A",
    "US4131575A",
    "US4001184A",
    "US4123436A",
    "US4636544A",
    "US5034458A",
    "US5387639A",
    "US5521230A",
    "US5672645A",
    "US5863974A",
    "US5866058A",
    "US5968561A",
    "US7790292B2",
    "US6255371B1",
    "US6605657B1",
    "US6609043B1",
    "US20020137827A1",
    "US6605659B2",
    "US7812077B2",
    "US7452944B2",
    "US20070290410A1",
    "US20070036964A1",
    "US7932310B2",
    "US7652107B2",
    "US20070179657A1",
    "US8263691B2",
    "US20090062436A1",
    "US9011982B2",
    "US8236227B2",
    "US8349933B2",
    "US8017699B1",
    "US8309637B2",
    "US8292610B2",
    "US20120252961A1",
    "US20130284991A1",
    "US20120251750A1",
    "US9283714B2",
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    "US20130224461A1",
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    "WO2015134316A1"
  ]
}

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