EP3004220A1 - Method for the thermal treatment of poly-arylene ether ketone ketone powders suitable for laser sintering - Google Patents
Method for the thermal treatment of poly-arylene ether ketone ketone powders suitable for laser sinteringInfo
- Publication number
- EP3004220A1 EP3004220A1 EP14731735.8A EP14731735A EP3004220A1 EP 3004220 A1 EP3004220 A1 EP 3004220A1 EP 14731735 A EP14731735 A EP 14731735A EP 3004220 A1 EP3004220 A1 EP 3004220A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- powder
- minutes
- pekk
- less
- ketone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B13/00—Conditioning or physical treatment of the material to be shaped
- B29B13/02—Conditioning or physical treatment of the material to be shaped by heating
- B29B13/021—Heat treatment of powders
-
- 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
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
- B29C67/02—Moulding by agglomerating
- B29C67/04—Sintering
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/124—Treatment for improving the free-flowing characteristics
-
- 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
- B29K2071/00—Use of polyethers, e.g. PEEK, i.e. polyether-etherketone or PEK, i.e. polyetherketone or derivatives thereof, as moulding material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
- C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
Definitions
- the present invention relates to a rapid process for heat treatment of polyarylene-ether-ketone-ketone powder suitable for laser sintering, as well as the powders resulting from this process.
- the present invention relates to a method for the thermal treatment of polyarylene-ether-ketone-ketone powders adapted to laser sintering. process.
- Polyarylene ether ketones and more particularly polyether ketone ketones (PEKK) are very effective materials. They are used for demanding applications in temperature and / or in mechanical stresses, even chemical. These polymers are found in fields as varied as aeronautics, offshore drilling, medical implants. They can be implemented by molding, extrusion, compression, spinning or laser sintering in particular. However, their implementation in the latter process requires powder preparation conditions ensuring good flowability in times prohibitive on the industrial level.
- Powder sintering technology under a laser beam is used to manufacture three-dimensional objects such as prototypes, models, but also functional parts, especially in the automotive, nautical, aeronautical, aerospace, medical (prosthetic, auditory systems) fields. , cellular tissues ...), textiles, clothing, fashion, decoration, housings for electronics, telephony, home automation, computers, lighting.
- a thin layer of powder is deposited on a horizontal plate held in a chamber heated to a certain temperature.
- the laser brings the necessary energy to sinter the powder particles at different points of the powder layer according to a geometry corresponding to the object, for example using a computer having in memory the shape of the object and restoring the latter in the form of slices.
- the horizontal plate is lowered by a value corresponding to the thickness of a layer of powder (for example between 0.05 and 2 mm and generally of the order of 0.1 mm) and then a new layer is deposited. of powder and the laser provides the energy necessary to sinter the powder particles in a geometry corresponding to this new slice of the object and so on.
- the procedure is repeated until the whole object has been made.
- An object surrounded by unsintered powder is obtained inside the enclosure. Parts that were not sintered therefore remained in powder form.
- the object is separated from the powder which can be reused for another operation.
- One of the conditions necessary to obtain a good operation of the laser sintering method consists of using powders having a good flowability necessary during the layering of the powder described above.
- US7847057 relates to a method of thermal treatment of poly-arylene-ether-ketone powders consisting of exposing the powder to a heat treatment greater than 30 minutes and of preferably greater than 1 hour, at a temperature of 20 ° C higher than the glass transition temperature of the polymer.
- WO2012047613 also describes a heat treatment applied more particularly to PEKK powders consisting of exposing the powder to a heat treatment lasting several hours between the transition temperatures of the different crystalline phases, more particularly by approaching the melting temperature of the polymer, corresponding to the crystalline form having the transition at the highest temperature.
- the flowability of the powder is improved and the resulting crystallinity of this treatment is retained during the sintering process, giving the sintered object some advantageous physical properties.
- the processing times are relatively long, typically several hours, which is industrially disadvantageous (machine occupation and low productivity).
- the invention relates to a process for the treatment of powders comprising PEKK, the measured flowability of which has a funneling time of 17 mm of less than 40 s, including the limit, preferably less than 30 s, and even more preferably less than 20 s. s, the flowability being measured as follows:
- the invention also relates to the powders obtained by such a process, as well as to the objects obtained by the process using such powders. Detailed description :
- polyarylene-ether-ketone ketones used in the invention comprise units of formulas IA, of formula IB and their mixture:
- polyarylene-ether-ketone-ketones corresponding to the generic names PEK, PEEKEK, PEEK, PEKEKK (or E denotes an ether function and K a ketone function) can not be ruled out, particularly when their use is combined with that of PEKK in proportions where the PEKK represents more than 50% in mass proportions and preferably more than 80% in proportions by mass, limits understood.
- the polyarylene ether ketone ketones are polyesters having a mixture of the units IA and IB such that the mass percentage of terephthalic unit by relation to the sum both the isophthalic and isophthalic units range from 55% to 85% and preferably from 55% to 70%, most preferably 60%.
- terephthalic and isophthalic unit is meant the formula of the acidic and isophthalic acids, respectively.
- These polyarylene-ether-ketone ketones are in the form of powders that may have been prepared by grinding or precipitation.
- the powders or powder mixtures used in the process which is the subject of the invention can be obtained for example by a grinding method described in application FR 1160258. They may optionally be additive or contain different compounds such as reinforcing fillers, especially mineral fillers such as carbon black, nanotubes, carbon or not, fibers, milled or not, stabilizing agents (light, in particular UV, and heat), agents facilitating the flow such as silica or optical brighteners, dyes, pigments or a combination of these fillers and / or additives.
- reinforcing fillers especially mineral fillers such as carbon black, nanotubes, carbon or not, fibers, milled or not
- stabilizing agents light, in particular UV, and heat
- agents facilitating the flow such as silica or optical brighteners, dyes, pigments or a combination of these fillers and / or additives.
- the treatment time will typically be strictly less than 30 minutes, ideally between 15 and 25 minutes while in a dynamic heating system such as a tube in which the powder and a hot gas circulates against the current, or a heated fluidized bed, a residence time of the order of a few minutes, may be sufficient, typically greater than 2 minutes but less than 30 minutes and preferably between 2 and 15 minutes.
- the treatment can also be performed in a pallet dryer, a dryer with a vertical axis, in a rotary kiln, or under a tunnel heated with infrared lamps.
- the powder resulting from this heat treatment is then used in a powder sintering device under a laser beam to allow the manufacture of an object.
- the use of such powders in processes such as rotational molding can not be ruled out. Examples:
- the powder is placed in a crystallizer so that the thickness of the powder bed is between 1 and 1.5 cm.
- the powders were sieved on a vibrating screen of 250 ⁇ m to de-agglomerate.
- the Dv50 referred to here is the volume median diameter which corresponds to the value of the particle size that divides the particle population examined in exactly two.
- the Dv50 is measured according to the ISO 9276 standard - parts 1 to 6. In the present description, a Malvern Mastersizer 2000 particle size analyzer is used, and the measurement is made in liquid way by laser diffraction on the powder. The results are given in Table 1 for residence times ranging from 15 minutes to 25 minutes.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1354917A FR3006317B1 (en) | 2013-05-30 | 2013-05-30 | PROCESS FOR THE HEAT TREATMENT OF POLYARYLENE-ETHER-KETONE-KETONE POWDERS ADAPTED TO LASER SINTERING |
PCT/FR2014/051242 WO2014191675A1 (en) | 2013-05-30 | 2014-05-27 | Method for the thermal treatment of poly-arylene ether ketone ketone powders suitable for laser sintering |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3004220A1 true EP3004220A1 (en) | 2016-04-13 |
Family
ID=48874364
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP14731735.8A Withdrawn EP3004220A1 (en) | 2013-05-30 | 2014-05-27 | Method for the thermal treatment of poly-arylene ether ketone ketone powders suitable for laser sintering |
Country Status (4)
Country | Link |
---|---|
US (2) | US20160122527A1 (en) |
EP (1) | EP3004220A1 (en) |
FR (1) | FR3006317B1 (en) |
WO (1) | WO2014191675A1 (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10882215B2 (en) | 2015-12-28 | 2021-01-05 | Arkema Inc. | Processes for producing polymer powders |
US10370530B2 (en) * | 2016-02-26 | 2019-08-06 | Ricoh Company, Ltd. | Methods for solid freeform fabrication |
FR3048430B1 (en) * | 2016-03-04 | 2019-08-30 | Arkema France | POLY- (ARYL-ETHER-KETONE) POWDER (PAEK) SUITABLE FOR SEVERAL TIMES IN SINTERING PROCESSES |
CN106752805B (en) * | 2017-01-25 | 2019-09-10 | 山东凯盛新材料股份有限公司 | The preparation method of coating polyether ketone ketone fine powder |
US11426928B2 (en) * | 2017-09-18 | 2022-08-30 | Solvay Specialty Polymers Usa, Llc | Additive manufacturing method for making a three-dimensional object using selective laser sintering |
EP3744751B1 (en) * | 2018-01-22 | 2022-08-17 | DIC Corporation | Polyarylene ether ketone resin and production method therefor, and molded article |
EP3825345A1 (en) * | 2019-11-19 | 2021-05-26 | Arkema France | Improved powder for additive manufacturing |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH661736A5 (en) * | 1984-12-12 | 1987-08-14 | Inventa Ag | MOLDING MATERIALS BASED ON THERMOPLASTIC, SATURATED HOMO OR MIXED POLYESTERS WITH REDUCED PROPERTY. |
KR20010050170A (en) * | 1999-08-31 | 2001-06-15 | 조셉 에스. 바이크 | Process for Bulk Handling Granular Polybutadiene |
DE102004062761A1 (en) * | 2004-12-21 | 2006-06-22 | Degussa Ag | Use of polyarylene ether ketone powder in a three-dimensional powder-based tool-less production process, and moldings produced therefrom |
WO2012047613A1 (en) * | 2010-09-27 | 2012-04-12 | Arkema Inc. | Heat treated polymer powders |
FR2982519B1 (en) * | 2011-11-10 | 2020-02-21 | Arkema France | PROCESS OF CRUSHING POLYARYL ETHER CETONES |
FR3006316B1 (en) * | 2013-05-30 | 2015-05-29 | Arkema France | COMPOSITION OF POLYARYLENE-ETHER-KETONE-KETONE POWDERS SUITABLE FOR LASER SINTERING |
-
2013
- 2013-05-30 FR FR1354917A patent/FR3006317B1/en not_active Expired - Fee Related
-
2014
- 2014-05-27 US US14/894,825 patent/US20160122527A1/en not_active Abandoned
- 2014-05-27 WO PCT/FR2014/051242 patent/WO2014191675A1/en active Application Filing
- 2014-05-27 EP EP14731735.8A patent/EP3004220A1/en not_active Withdrawn
-
2017
- 2017-12-04 US US15/830,100 patent/US20180148572A1/en not_active Abandoned
Non-Patent Citations (2)
Title |
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None * |
See also references of WO2014191675A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO2014191675A1 (en) | 2014-12-04 |
US20180148572A1 (en) | 2018-05-31 |
FR3006317A1 (en) | 2014-12-05 |
US20160122527A1 (en) | 2016-05-05 |
FR3006317B1 (en) | 2016-06-24 |
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RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: BRULE, BENOIT Inventor name: STER, HERVE Inventor name: HUZE, DENIS Inventor name: DECRAEMER, NADINE Inventor name: PASCAL, JEROME |
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