EP4355555A1

EP4355555A1 - Additive manufacturing method, polymer powder composition comprising a detection additive, and object obtained by the method

Info

Publication number: EP4355555A1
Application number: EP22743558.3A
Authority: EP
Inventors: Olivier COULET; Rita FETEIRA ESCUDEIRO; Arnault COULET
Original assignee: Fabulous
Current assignee: Fabulous
Priority date: 2021-06-17
Filing date: 2022-06-14
Publication date: 2024-04-24
Also published as: DE212022000027U1; DK4355555T1

Abstract

The invention relates to a method for manufacturing a three-dimensional object, comprising locally raising the temperature of a powder using electromagnetic radiation in a heated chamber, causing the localised melting/coalescing of a layer of a predetermined thickness in order to form, after cooling, a solid polyamide layer, the method being characterised in that the powder comprises, relative to the total weight of the composition: - between 60% and 99% by weight of polyamide; - between 1% and 40% by weight of an optical and/or magnetic detection additive selected from the group formed by: pigments comprising a spinel structure containing a cation of a transition metal, the oxides of a transition metal, the sulphides of a transition metal; - between 0% and 5% by weight of a flow agent and in that the powder has: - a particle size distribution D₅₀ of between 35 μm and 55 pm; and - a particle size distribution D₁₀ of more than 15 μm; and - a particle size distribution D₉₀ of less than 100 μm.

Description

ADDITIVE MANUFACTURING METHOD, POLYMER POWDER COMPOSITION COMPRISING A DETECTION ADDITIVE, AND OBJECT OBTAINED BY SAID METHOD

TECHNICAL FIELD OF THE INVENTION

The present invention relates to the manufacture of parts made of polymer materials and relates to a process for agglomeration, layer by layer, in particular by melting or sintering, of a polymer powder comprising an optical and/or magnetic detection additive. The present invention also relates to such a polymer powder supplied for this process and consumed during the process. The present invention finally relates to an object obtained by the process which has particularly advantageous properties in the field of the safety of food production lines.

STATE OF THE ART

Among the wide variety of additive manufacturing technologies for parts made of polymer materials now available, the present application falls within the scope of technologies involving an agglomeration of powder, layer by layer, in order to obtain a three-dimensional object. Thus, in the context of this document, the terms “additive manufacturing” or “3D printing” only designate these methods. “3D object” will designate an object obtained by such a 3D printing method.

In this context, the agglomeration of powders by fusion, coalescence, and/or “sintering”, is caused by radiation making it possible to melt the material to be agglomerated. For example, selective laser sintering (SLS, abbreviated to “Selective Laser Sintering”) consists in locally densifying a material presented in powder form, by melting it under the action of a laser. Any other source of electromagnetic radiation making it possible to melt the powder can also be implemented, for example infrared, visible or UV radiation. Other notable powder bed fusion additive manufacturing methods include laser sintering, Multi Jet Fusion, infrared radiation sintering and high speed sintering in particular.

The use of 3D objects made of thermoplastics is advantageous in industrial production chains, in particular because such objects can be produced in small series for specific uses or because they have specific structural features. However, 3D objects made of thermoplastics are difficult to detect by means of detection of foreign bodies usually implemented in the context of on-line quality control, in particular in the food industry. So if a 3D object made of thermoplastics breaks, fragments can end up in the product and represent a risk for food safety.

The additive manufacturing processes known from the prior art and the powders they use do not make it possible to produce 3D objects that have both satisfactory mechanical properties for use in industry and strong detectability by means of detection of foreign bodies, for example by magnetic detection or by detection of an unusual color.

DETAILED DESCRIPTION OF THE INVENTION

The present invention aims to remedy all or part of these drawbacks.

To this end, according to a first aspect, the present invention relates to a method for manufacturing a three-dimensional object, comprising a local rise in the temperature of a polyamide-based powder by electromagnetic radiation in a heated enclosure, causing the melting localized layer of a predetermined thickness to form, after cooling, a solid layer of polyamide, said method being characterized in that said powder comprises, over the total weight of the composition:

- between 60% and 99% by weight of polyamide;

- between 1% and 40% by weight of an optical and/or magnetic detection additive selected from the group formed by: pigments comprising a spinel structure which contains a cation of a transition metal, sulphides of a metal of transition ;

- between 0% and 5%, and preferably between 0.1% and 4.5%, by weight of a flow agent; and in that the powder has:

- a D ₅₀ particle size distribution of between 35 μm and 55 μm; and

- a D ₁₀ particle size distribution greater than 15 μm and

- a D ₉₀ particle size distribution of less than 100 μm.

In embodiments, the powder has:

- a D ₅₀ particle size distribution between 35 μm and 55 μm,

- a D ₁₀ particle size distribution of between 15 μm and 25 μm and

- a D ₉₀ particle size distribution of between 80 μm and 100 μm. In some embodiments, the particle size distribution D ₁₀ is greater than 10 μm, preferentially greater than 15 μm, preferentially greater than 17 μm, preferentially greater than 20 μm.

In embodiments, the particle size distribution D ₅₀ is less than 110 μm, preferably less than 100 μm, preferably less than 95 μm, preferably less than 93 μm, preferably less than 90 μm. In embodiments, the particle size distribution D ₅₀ is less than 80 μm.

In some embodiments, a mass fraction comprised between 30% and 70% of said powder is fresh polyamide powder, and a mass fraction comprised between 70% and 30% of said powder is polyamide powder recovered in said enclosure heated to the end of a previous manufacture, and said fresh polyamide powder has an internal viscosity index measured according to ISO 307:2019 of between 0.9 deciliters per gram and 1.4 deciliters per gram, at 25°C.

In some embodiments, the electromagnetic radiation causing the localized melting of a layer is laser radiation with an energy density greater than or equal to 25 mJ/mm ² . The method used in this case is preferably the selective laser sintering method, more often called SLS (abbreviated to “Selective Laser Sintering”).

According to a second aspect, the invention relates to a powder composition for an additive manufacturing process characterized in that it comprises, over the total weight of the composition:

- between 60% and 99% by weight of polyamide;

- between 1% and 40% by weight of a detection additive, preferably an optical detection additive and/or a magnetic detection additive, selected from the group formed by: pigments comprising a spinel structure which contains a cation of a transition metal, oxides of a transition metal, sulfides of a transition metal;

- a D ₅₀ particle size distribution of between 35 μm and 55 μm; and

- a D ₁₀ particle size distribution greater than 15 μm and

- a D ₉₀ particle size distribution of less than 100 μm. In embodiments, the powder composition of the invention is obtained by dry mixing a natural polyamide powder with a polyamide powder comprising a detection additive.

In embodiments, the powder composition that is the subject of the invention comprises:

- between 0.05% and 5% by weight of an optical detection additive chosen from pigments comprising a spinel structure which contains a cation of a transition metal and

- between 1% and 35% by weight of a magnetic detection additive among the oxides of transition metals.

Alternatively, the optical or magnetic detection additive is chosen from sulphides of a transition metal.

In embodiments, the powder composition that is the subject of the invention has an internal viscosity index measured according to ISO 307:2019 of between 0.9 deciliters per gram and 1.4 deciliters per gram.

In some embodiments, the powder composition that is the subject of the invention has a value ΔT=(T _m −T _c ) _onset , of between 30°C and 50°C.

In some embodiments, the powder composition that is the subject of the invention comprises an optical detection additive and said optical detection additive comprises cobalt blue.

According to a third aspect, the invention relates to a three-dimensional object obtained by additive manufacturing from a composition that is the subject of the invention.

In embodiments, the three-dimensional object is colored blue in the mass by an optical detection additive. Preferably, the optical detection additive allows optical detection in a wavelength range between 0.5 μm and 12 μm.

In embodiments, the three-dimensional object has a modulus of elasticity greater than or equal to 1700 MPa, a tensile strength greater than or equal to 30 MPa, an elongation at break greater than or equal to 20% according to a first orientation and greater than or equal to 35% on a second orientation perpendicular to the first.

BRIEF DESCRIPTION OF FIGURES

Other advantages, aims and particular characteristics of the invention will emerge from the non-limiting description which follows of at least one mode of particular embodiment of the additive manufacturing process, of the powder composition for said process and of a three-dimensional object obtained by said process, objects of the present invention, with reference to the appended drawings, in which:

[Fig 1] represents particle size distribution density curves as a function of the particle size of two powder compositions according to the invention and of a natural polyamide 11 powder,

[Fig 2] represents cumulative distribution curves as a function of circularity for two powder compositions according to the invention and a natural polyamide 11 powder,

[Fig 3] represents a view captured with a scanning electron microscope of a powder composition according to the invention,

[Fig 4] represents a view obtained by X-ray tomography of a section of a 3D object obtained at the end of the additive manufacturing process from the powder composition illustrated in figure 3,

[Fig 5] schematically represents a section of a 3D object obtained by sintering the powder composition illustrated in figure 3,

[Fig 6] represents a view captured under a scanning electron microscope of a powder composition for additive manufacturing,

[Fig 7] represents a view obtained by X-ray tomography of a section of a 3D object obtained at the end of the sintering process of the powder composition illustrated in Figure 6,

[Fig 8] schematically represents a section of a 3D object obtained by sintering the powder composition illustrated in figure 6,

[Fig 9] represents a DSC differential scanning calorimetry of a particular powder composition according to the invention,

[Fig 10] represents a graph of the force in MPa as a function of the elongation along an xy orientation, expressed in %, obtained at the end of an elongation test on a 3D object obtained by sintering a composition of powder A, according to a particular embodiment of the invention,

[Fig 11] represents a graph of the force in MPa as a function of the elongation along an xz orientation, expressed in %, obtained at the end of a test of elongation on a 3D object obtained by sintering a powder composition A, according to a particular embodiment of the invention and

[Fig 12] represents a graph which shows the volumetric particle size distribution as a function of the particle size of a powder composition according to the invention.

DESCRIPTION OF EMBODIMENTS OF THE INVENTION

This description is given on a non-limiting basis, each characteristic of an embodiment being able to be combined with any other characteristic of any other embodiment in an advantageous manner.

The values of the internal viscosity index of the polyamide given in this document refer to the ISO 307:2019 standard and at a temperature of 25°C.

The powder composition for additive manufacturing process by sintering according to the invention comprises, over the total weight of the composition:

- between 60% and 99% by weight of polyamide,

- between 1% and 40% by weight of a detection additive, which may be an optical detection additive and/or a magnetic detection additive, and which is preferably selected from the group formed by: pigments comprising a structure spinel which contains a cation of a transition metal, the oxides of a transition metal, the sulphides of a transition metal;

- between 0% and 5% and preferably between 0.1% and 4.5% by weight of a flow agent: and in that the powder has:

- a D ₅₀ particle size distribution of between 35 μm and 55 μm; and

- a D ₁₀ particle size distribution greater than 15 μm and

- a D ₉₀ particle size distribution of less than 100 μm.

The powder is said to be “polyamide-based” because it mainly comprises polyamide.

The characteristics of the powder composition for additive manufacturing process by sintering, hereinafter "sintering powder", and of its components are detailed below.

The shape of the grains of the sintering powder is preferably spherical.

According to the invention, said detection additive can be selected so as to allow magnetic detection or optical detection, or one can using two additives, namely a first additive allowing magnetic detection and a second additive allowing optical detection, or else an additive is used allowing both optical detection and magnetic detection.

Choice of polvamide or mixture of polyamides

The polyamide can be chosen from any available polyamide, or mixture of polyamides, making it possible to obtain the particle size characteristics of the composition of the invention.

Preferably, the polyamide is chosen from polyamides comprising one of the following monomers: PA6, PA10, PA11, PA12 and mixtures thereof.

In particular, PA11 can be used for its advantageous characteristics and its biosourced origin. We call “biobased” a product that is entirely or partially made from materials of biological origin.

Characteristics of the sintering powder and working temperature T ₂ )

Preferably, the sintering powder has a working temperature window of between 160°C and 210°C. The working temperature window is the temperature interval delimited by the extrapolated initial temperature of the melting peak (T _ei.m or T _m,onset in °C) and the extrapolated final temperature of the crystallization peak (T _ef,C or T _c , _onset in °C). The difference between these two temperatures is called ΔT, it expresses as follows ΔT- T _ei.m -T _ef.c or ΔT=

(Tm~T _c ) _onset.

The extrapolated initial temperature of the melting peak Tm, _onset and the extrapolated final temperature of the crystallization peak T _c,onset will be better understood by reading the article Polymers Applicable for Laser Sintering (LS), published by Schmid M. & Wegener K in 2016 (Additive Manufacturing: Procedia Engineering, 149, 457-464), particularly with regard to figure 9.

Preferably, ΔT=(T _m ~T _c ) _onset is between 30°C and 50°C. This ΔT is advantageous because it makes it possible to define the working temperature Tg. More preferably still, ΔT=(T _m ~T _c ) _onset is between 30°C and 35°C.

In the case of a ΔT lower than 30°C, the polymer risks overreacting to the change of state by the supply of energy.

For a ΔT greater than 50° C. the risk is of not being able to define its stable working temperature T ₂ , and consequently of obtaining a general agglomeration of the powder bed and problems of covering. Similarly, it is necessary to adapt the energy supply as a function of the working temperature T ₂ chosen in this range ΔT=(T _m −T _c ) _onset. Excessive energy input would have the negative consequence of deforming the 3D printed object.

Detection additive

According to an essential characteristic of the invention, the powder composition comprises a detection additive. This additive is advantageously an inorganic compound which is insoluble in water and non-toxic, preferably of the spinel type. The powder composition of the invention comprises, on the total weight of the composition, between 1% and 40% by weight of a detection additive.

The detection additive may be an optical detection additive. More particularly, the powder composition of the invention may comprise, relative to the total weight of the composition, between 0.05% and 5% by weight of an optical detection additive, for example between 0.05% and 0 .5%. The latter is advantageously selected from pigments comprising a spinel structure which contains a cation of a transition metal. This type of pigment has the advantage of not being toxic. In particular, the transition metal cation remains trapped in the spinel structure and cannot be dissolved under normal conditions of contact with food and drink, nor in the event of accidental ingestion through the intestinal transit. Spinels have good thermal stability under the laser beam implemented in the SLS laser sintering process technique. The implementation of these pigments is therefore particularly preferable for the powder compositions intended for this use.

According to a particular embodiment, the pigment is a blue pigment, preferably cobalt aluminate (CAS No: 1345-16-0), which is available under the trade name PB 28. Preferably, the detection additive optics used allows optical detection, if necessary by infrared. For example, the optical detection additive used allows optical detection in a wavelength range between 0.5 μm to 12 μm.

According to other embodiments, the pigment comprises an olivine structure or a rutile structure.

It is specified that the optical detection additive is present in a substantially homogeneous manner in the powder composition, such that the parts obtained by additive manufacturing from this powder are colored in the mass. The detection additive can be a magnetic detection additive. More particularly, the powder composition of the invention may comprise, relative to the total weight of the composition, between 1% and 40% by weight of a magnetic detection additive.

The magnetic detection additive is preferably chosen from oxides comprising a transition metal. For example, the magnetic detection additive is an iron oxide, such as natural or synthetic magnetite (Fe ₃ O ₄ ). This spinel-like oxide is insoluble in water and non-toxic. In addition, it is not likely to form metal salts likely to be released by parts obtained by additive manufacturing from this powder. Natural magnetite will be preferred to synthetic magnetite.

Whether as an optical detection additive or as a magnetic detection additive, it is also possible to use an oxide of a transition metal which is not a spinel, or else a sulphide of a metal of transition. Magnetic detection additives must of course be selected to have particular magnetic properties that can be easily detected.

In a preferred embodiment, the powder composition of the invention comprises both between 0.05% and 5% by weight of an optical detection additive chosen from pigments comprising and between 1% and 40% by weight of a magnetic detection additive among the oxides of the transition metals.

Choice of flow agent

The composition of the invention further comprises a flow agent in sufficient quantity for the composition to flow freely, remain fluid and form a uniform, homogeneous and flat layer during the generative layering process in a PBF powder bed (Powder Bed Fusion) for example called layer by layer sintering of SLS, LS polymers.

The composition of the invention comprises, on the total weight of the composition, between 0% and 5% by weight of a flow agent. A content between 0.1% and 4.5% by weight is preferred.

The flow agent is chosen from those commonly used in the field of sintering polymer powders, for example from: silicas, precipitated silicas, silica fumes, hydrated silicas, vitreous silicas, fumed silicas, vitreous phosphates, vitreous oxides.

Preferably the flow agent has a low contact surface.

Manufacture of a powder composition

According to a particular embodiment, the powder composition in accordance with the invention is obtained according to a manufacturing method which comprises a first step of mixing a so-called "natural" polyamide powder with a flow agent and at least one one of the following steps:

- a step of mixing the composition obtained previously with a polyamide powder composition comprising an optical detection additive;

- a step of mixing the composition obtained previously with a composition comprising a magnetic detection additive.

In particular embodiments, these last two steps of mixing with a composition comprising a detection additive are implemented successively, it is noted that their order can be reversed.

A natural polyamide powder is a powder composition comprising between 95% and 100% polyamide, preferably at least 99% by weight of polyamide.

The polyamide powder composition comprising an optical detection additive can be obtained by reduction to powder of a homogeneous liquid or solid mass comprising the polyamide and said optical additive or by polycondensation in the solid phase, drying then selective grinding.

The composition comprising a magnetic detection additive can either be the magnetic additive in pure form (that is to say comprising at least 95% of magnetic detection additive) or be a composition comprising a polyamide homogenized by dry mixing with a magnetic sensing additive.

The mixing steps mentioned above can be carried out by dry blending (known by the English term “dry blend”) or by a compounding process (known by the English term “master batch”). Compounding requires a subsequent stage of selective grinding of the mass obtained and adjustment of the viscosity by polycondensation in the solid phase and drying; for this reason dry mixing is preferred. The dispersion of the flow agent requires the application of significant mixing energy to obtain good homogenization. This mixing energy is likely to damage the detection additives. It is therefore preferentially opted for a dry premix of the flow agent with a natural polyamide powder during the first mixing step, prior to at least one step of mixing with a composition comprising a detection additive, of less intensity than the first.

In embodiments, the mixing steps are carried out by cryogenic grinding, this method well known to those skilled in the art is not described in detail here.

In these other embodiments, the methods for obtaining a dry mixture of homogeneous and dispersed powder of all the components are adapted according to the initial distributions and the final target distribution, i.e.:

- a D ₅₀ particle size distribution between 35 μm and 55 μm,

- a D ₁₀ particle size distribution of between 15 μm and 25 μm and

- a D ₉₀ particle size distribution of between 80 μm and 100 μm.

According to a particular embodiment, the final target particle size distribution of the powder has:

- a D ₅₀ particle size distribution of between 35 μm and 55 μm, and

- a D ₁₀ particle size distribution greater than 20 μm and

- a D ₉₀ particle size distribution of less than 80 μm.

Particle size distribution of the powder composition

The particle size distribution D ₁₀ of the powder composition is greater than 10 μm, preferentially greater than 15 μm, preferentially greater than 17 μm, preferentially greater than 20 μm.

Such a particle size distribution D ₁₀ of the powder composition is advantageous for avoiding the presence of too large a quantity of fine particles or dust liable to volatilize into the air and to present a health risk in the event of inhalation and accumulation, eye irritation and skin contact of these fine dusts.

The D ₅₀ particle size distribution of the powder composition is between 35 μm and 55 μm. Preferably, the particle size distribution D ₅₀ of the powder composition is between 38 μm and 45 μm, very preferably it is between 38 μm and 40 μm. The applicant has observed during its tests that these D ₅₀ particle size distribution ranges make it possible to obtain the best performance in terms of final resolution, geometric definition of the parts obtained as well as better coverage and good fluidity of the powder in temperature for the PBF powder bed process using layers from 80 μm to 120 μm.

The particle size distribution D ₉₀ of the powder composition is less than 110 μm, preferably less than 100 μm, preferably less than 95 μm, preferably less than 93 μm, preferably less than 90 μm. In embodiments, the particle size distribution D ₅₀ is less than 80 μm.

Such a particle size distribution D ₉₀ is advantageous for an implementation of the powder in an additive manufacturing process whose layer thickness is between 80 μm and 160 μm, for example for a layer thickness of 100 μm. Preferably, the D ₉₀ is chosen to be less than the layer size envisaged for the additive manufacturing process.

According to a particular embodiment, the powder composition has:

- a D ₅₀ particle size distribution between 35 μm and 55 μm,

- a D ₁₀ particle size distribution of between 15 μm and 25 μm and

- a D ₉₀ particle size distribution of between 80 μm and 100 μm.

The applicant has found that such particle size distributions D ₁₀ , D ₅₀ , and D ₉₀ are advantageous because, while it is advantageous to have a narrow distribution and of the same morphology for additive manufacturing by sintering, too great a homogeneity of particle size of the powder composition gives rise to “caking” phenomena (that is to say powder agglomeration) because geometric arrangements make the powder more agglomerated. Thus, these particle size distributions D ₁₀ , D ₅₀ , and D ₉₀ are advantageous because they make it possible to limit the phenomena of powder agglomeration and make it easier to depowder parts obtained by additive manufacturing by sintering.

The particle size distribution values of the powder composition D ₁₀ , D ₅₀ and D ₉₀ mentioned above are determined by the static image analysis method according to standard ISO 13322-1:2014.

Figure 1 shows the distribution density curves as a function of particle size (expressed in micrometers, abbreviated as μm) for three powders:

- a curve 105 illustrates the particle size distribution of a PA11 powder called natural, that is to say comprising at least 99% of PA11,

- a curve 110 illustrates the particle size distribution of a composition A of powder according to the invention, in which the polyamide is a PA11 and which comprises an optical detection additive,

- a curve 115 illustrates the particle size distribution of a powder composition B according to the invention, in which the polyamide is a polyamide 11 and which comprises both an optical detection additive and a magnetic detection additive.

It is emphasized that the optical detection additive and/or the magnetic detection additive are selected with a view to obtaining a particle size distribution of the powder composition as detailed above. Thus, it is seen in Figure 1 that the particle size distribution of the powder compositions according to the invention, with detection additive, remain close to that of the particle size distribution of the distribution of the natural PA11 powder, with a density peak around 50μm.

Advantageously, the powder composition which is the subject of the invention comprises 90%, more preferentially 99%, of grains whose size is between 10 μm and 120 μm, preferentially between 20 μm and 90 μm, very preferentially between 20 μm and 80 μm .

A graph is observed in FIG. 12 which shows the particle size distribution as a function of the size of the particles of the powder composition A, in which the polyamide is a PA11 and which comprises an optical detection additive. The data illustrated in FIG. 12 come from particle size measurements carried out using a Mastersizer 3000 (registered trademark) particle size analyzer from Malvern Panalytical. The graph presents bars 140 of a histogram illustrating the percentage of particles in the powder composition associated with each size, expressed in μm. A curve 150 illustrates the cumulative percentage of particles whose size is less than a threshold, expressed in μm. It can be seen in the graph of FIG. 12 that the powder composition A comprises 90% of grains whose size is between 10 μm and 120 μm.

Powder Composition Form Factors

Shape factors are dimensionless quantities used in image analysis and microscopy that numerically describe the shape of a particle, independent of its size.

The circularity/wax index is a form factor which is calculated as follows: [Math 1] where P is the perimeter and A looks like an image of a grain of powder

Thus a sphere which will have a circularity index of 1 while a mica, of parallelepiped shape will have a circularity close to 0.

The rules and nomenclature for the description and quantitative representation of particle shape and morphology specified by ISO 9276-6:2008 are followed here.

Preferably, the cumulative distribution f ₁₀ of the powder composition according to the invention is less than or equal to 0.15. Very preferably, the cumulative distribution fio of the powder composition is less than or equal to 0.10. In other words, only 10% of the powder grains have a circularity index less than or equal to 0.15, preferably less than or equal to 0.10. In other words, 90% of the grains have a circularity index greater than 0.1, preferably greater than 0.15.

The f ₅₀ cumulative distribution of the powder composition is less than or equal to 0.6. Preferably, the f ₅₀ cumulative distribution of the powder composition is less than or equal to 0.55. In other words, only 50% of the powder grains have a circularity index less than or equal to 0.6, preferably less than or equal to 0.55. In other words, 50% of the powder grains have a circularity index greater than 0.55, preferably greater than 0.6.

The f ₉₀ cumulative distribution of the powder composition is less than or equal to 0.8. Preferably, the f ₉₀ cumulative distribution of the powder composition is less than or equal to 0.75. In other words, 90% of the powder grains have a circularity index less than or equal to 0.8, preferably less than or equal to 0.75. In other words, 10% of the powder grains have a circularity index greater than 0.75, preferably greater than 0.8.

FIG. 2 shows a graphical representation of the cumulative distribution on the ordinate (expressed as a percentage), as a function of the circularity on the abscissa (index without unit). We observe in figure 2:

- a curve 205 illustrating the cumulative distribution of a so-called natural PA11 powder, that is to say comprising at least 99% by mass of PA11, - a curve 210 illustrates the cumulative distribution of a powder composition according to the invention, in which the polyamide is a PA11 and which comprises an optical detection additive,

- a curve 215 illustrates the cumulative distribution of a powder composition according to the invention, in which the polyamide is a polyamide 11 and which comprises both an optical detection additive and a magnetic detection additive.

The optical detection additive and/or the magnetic detection additive are preferably selected with a view to obtaining a cumulative distribution of the powder composition as detailed above. It can thus be seen in FIG. 2 that the cumulative distribution of the powder compositions according to the invention, with detection additive, remain close to that of the particle size distribution of the distribution of the natural PA11 powder.

The morphology of the grains is important for the fluidity of the mixture and for the densification of the powder bed during successive coatings, but also for the residual porosity in the final parts obtained. A good sphericity of the powder combined with a very tight distribution, that is to say a cumulative distribution of the type presented above, make it possible to obtain a natural densification of the powder bed by compaction and by geometric arrangements of layer. This layer is then exposed to laser energy for melting and coalescence promoting the densification of parts with low residual porosity. Conversely, a very heterogeneous powder with a wider distribution will tend to organize itself in a more chaotic way and will cause less densification of the powder bed, as some of the larger grains may not be melted.

To illustrate this point, FIGS. 3 and 6 show two views captured under a scanning electron microscope of two powders, at the same magnification. FIG. 3 illustrates a powder which has a sphericity comparable to the sphericity of a powder composition which is the subject of the invention, that in FIG. 6 is presented by way of comparison.

These powders are subjected to an SLS laser sintering process at an energy density of 34 mJ/mm ² (550 and 850). X-ray tomography views of the sections of 3D objects obtained at the end of the sintering process are presented in FIGS. 4 and 7. A schematic representation of the powders 30 and 60 illustrated in FIGS. 3 and 6 and of sections of objects 3D images obtained by sintering these powders are presented in figures 5 and 8. The powder 30 illustrated in FIG. 3 is a powder with a good homogeneity of circularity with a circularity of the grains comprised between 0.4 and 0.8, on average equal to 0.65. The powder 30, placed on a previously solidified layer 505 and subjected to an SLS laser sintering process 550 at an energy density of 34 mJ/mm ² makes it possible to obtain a low and distributed residual porosity, as illustrated in section 410, in figure 4, obtained by tomography of the 3D object and on the section 510, in figure 5. The porous parts 420 which appear in black in figure 4 are illustrated in the form of white cavities in figure 5. These porous parts are less numerous and better distributed than those observed on the sections of a 3D object obtained by sintering from a powder of less homogeneity of circularity of the grains, represented in figures 7 and 8.

The powder 60 illustrated in FIG. 6 has less homogeneity than the homogeneity of the powder 30, with a grain circularity of between 0.1 and 0.8, on average equal to 0.55. The powder 60, placed on a previously solidified layer 805 and subjected to an SLS laser sintering process 550 at an energy density of 34 mJ/mm ² results in obtaining a 3D object of less good homogeneity and residual porosity larger, presented in section 710 obtained by tomography, in figure 7, and in schematic section 810 in figure 8.

3D object manufacturing process

It is recalled that the present application falls within the framework of technologies involving a bed of powder with an agglomeration layer by layer, with a view to obtaining a three-dimensional object. Thus, in the context of this document, the terms “additive manufacturing” or “3D printing” only designate these methods. “3D object” will designate an object obtained by such a 3D printing method.

The present invention relates more particularly to an additive manufacturing process by powder bed fusion (PBF, abbreviated to Power Bed Fusion), layer by layer, from a polyamide powder in a heated enclosure. These methods include in particular laser sintering (LS = Laser Sintering), selective laser sintering (SLS = Selective Laser Sintering), Multi Jet Fusion (MJF = Multi Jet Fusion), infrared radiation sintering (IRS = Infrared Sintering ) and high-speed sintering (HSS). Regardless of the additive manufacturing method chosen, the method of the invention relates to the manufacture of 3D objects in polyamide comprising a detection additive, from a composition of polyamide powder.

The method according to the invention takes place in a closed chamber preheated to a setpoint temperature T ₁ . The atmosphere inside the enclosure is enriched in nitrogen (or under vacuum) and depleted in oxygen, in order to limit the oxidation of the polymer powder; this oxidation gradually leads to the elongation of the macromolecules constituting the particles of polymer powder and represents the main aging mechanism of said powders. This elongation of the macromolecules tends to increase the internal viscosity of the polymer. The limitation of the temperature oxidation of the powders promotes the recycling of the unused powder, which contributes significantly to the economy of the process according to the invention. Preferably, the oxygen level is less than 5% by volume, preferably less than 2%, and even more preferably less than 1%.

The holding temperature T ₁ is advantageously around 20 to 30 degrees around the crystallization temperature Te of the polymer. According to an advantageous embodiment, for a powder based on PA11 and/or PA12 polyamide, the preheating temperature T ₁ is advantageously between about 140°C and about 160°C, preferably between about 142°C and about 158°C. °C. According to embodiments, the heating temperature is equal to the holding temperature.

More generally, the holding temperature T ₁ is preferably between 150 and 185° C.

The process which is the subject of the invention comprises the deposition of a uniform layer of a bed of polyamide powder in a preheated chamber.

Immediately after the deposition of each layer, the surface of the powder bed is heated rapidly, typically by infrared radiation, to a temperature T ₂ which is selected to be approximately 8% to 14% lower than the T _m of the polyamide (i.e. 12 to 26 degrees below the melting temperature T _m of the powder). This heating to a temperature T ₂ makes it possible to maintain the polyamide powder at a temperature quite close to its melting temperature, without however reaching this melting temperature. We also speak of working temperature for PBF systems. According to an advantageous embodiment, for a powder based on polyamide PA11 and/or PA6, the temperature T ₂ is between about 183°C and about 204°C.

More generally, the temperature T ₂ is between 168°C and 206°C.

The melting of the powder is necessary to obtain a compact part. This melting must be transitory, rapid, localized and controlled, so as to avoid the uncontrolled flow of the liquid polymer; for this reason it must be brief, that is to say that the localized melting must be followed promptly by cooling to a temperature below the melting point T _m of the polymer, towards a temperature T _R at which the polymer can recrystallize from the molten state. Said temperature TR may be in the vicinity of temperature T ₂ , it is between T ₁ and T ₂ .

To obtain said localized and controlled melting of a selected part of the powder bed, electromagnetic radiation irradiates targeted zones of the polyamide powder, making it possible to locally increase the temperature and to agglomerate between them the polyamide grains of the targeted zones . Depending on the method chosen, the electromagnetic radiation is for example visible, infrared or near infrared laser radiation. The local temperature T _L of the melting zone is preferably approximately 8% to 14% higher than the T _m of the polyamide (ie 12 to 26 degrees higher than the melting temperature T _m of the powder). A transient liquid phase is thus formed, but if T _L is too high, the viscosity of the molten polymer becomes too low and there is a risk of running.

By way of specific examples, the temperatures T ₁ and T ₂ implemented during a sintering process according to the invention are collated in table 1 below and compared with the melting point T _m and the crystallization temperature T _c of the sintering powders A and B according to the invention.

[Table 1] It is specified that:

- powder A is a powder composition according to the invention, in which the polyamide is a PA11 and which comprises an optical detection additive and

- powder B is a powder composition according to the invention, in which the polyamide is a polyamide 11 and which comprises both an optical detection additive and a magnetic detection additive.

For the determination of any interval centered on the melting temperature or the crystallization temperature, one will more preferably use an extrapolated initial temperature of the melting peak (T _m , _onset ) and the extrapolated final temperature of the crystallization peak (T _c , _onset ), rather than the temperature values corresponding to the melting and crystallization peaks, although the two methods for determining these reference values can be implemented without deviating from the invention.

To illustrate this, FIG. 9 shows a DSC (Differential Scanning Calorimetry) of a powder composition according to the invention based on PA11. This DSC shows a curve 910 of initial temperature rise and a curve 920 of cooling. Melting and crystallization temperatures are shown in this graph, whether determined by identification of the corresponding peak (T _c and T _m ) or at the extrapolated initial temperature for the melting peak (T _m , _onset ) and at the extrapolated final temperature for the crystallization peak (T _c.onset ).

Once all of the targeted areas of a powder bed layer have been swept by the electromagnetic radiation source, a new powder bed is deposited and flattened on top of the previous one. It is recalled that the powder is self-supporting, that is to say that it rests on the powder previously deposited during the process. So on, a new powder bed is deposited and the solidification of part of the new powder bed is initiated. The solidified part of each powder bed corresponds to a layer or slice of the 3D object obtained at the end of the process.

The thickness of each slice is typically between about 50 μm and about 150 μm, preferably between about 70 μm and about 120 μm, and even more preferably between about 80 μm and about 110 μm. The deposition of each slice is followed by heating to the temperature T ₂ , as described above. According to one embodiment of the process, the sintering which is the subject of the invention is carried out by SLS and the electromagnetic radiation causing the localized melting of a layer is laser radiation with an energy density greater than or equal to 25 mJ/mm ² for a working temperature T ₂ of between 180°C and 199°C, for example equal to 188°C. The energy density greater than or equal to 25 mJ/mm ² makes it possible to avoid the delamination of layers, that is to say the separation between two successive layers of solidified polyamide.

Energy density is calculated using Morgan's simplified formula, which is expressed as follows:

[Math 2] where P is the laser power, expressed in Watts

S is the spacing between scans (Hatch Gap), expressed in millimeters (mm) v is the laser speed, expressed in mm/second r is the laser radius, expressed in mm

By way of examples, the operating conditions of sintering processes according to the invention with different SLS systems are collated in Table 2 below. These operating conditions are implemented on a sintering powder composition comprising PA 11 , with a fixed layer thickness of 100 μm, at a working temperature T ₂ approximately equal to 188°C.

[Table 2] The 3D object at the end of the sintering process is covered with non-agglomerated powder, this powder is removed by mechanical and/or chemical means well known to those skilled in the art (air or water jet, brushing, sandblasting , treatment in solvent phase, ultrasonic bath, treatment with an HF solution, etc.) which are not detailed here.

Reuse of the polyamide powder composition object of the invention

During a process such as that described above, part of the powder composition for additive manufacturing process by powder bed PBF (Power Bed Fusion) according to the invention introduced into the heating chamber is not solidified. Advantageously, this powder is collected and sieved with a view to its reuse as a mixture with a composition of fresh polyamide powder, that is to say with a powder which has not already been used in a sintering process.

Preferably, the powder composition according to the invention comprises a mass fraction of between 20% and 70% of fresh polyamide powder composition, and a mass fraction of between 80% and 30% of polyamide powder recovered at the end of a previous production. More preferably, the deposited powder bed comprises a mass fraction of between 25% and 55% of fresh polyamide powder composition, and a mass fraction of between 75% and 45% of polyamide powder recovered after a previous production.

Adding fresh powder to spent powder adds undamaged (non-thermo-oxidized) polyamide grains, which are not already damaged or deformed by a previous thermo-oxidation-inducing sintering process, and thus maintains viscosity internal mixture within a given range by lowering this viscosity with each cycle as it evolves.

Preferably, the fresh polyamide powder used has an internal viscosity index measured according to ISO 307:2019 of between 0.9 deciliters per gram and 1.4 deciliters per gram. An internal viscosity index of less than 1.4 deciliters per gram, preferably less than 1.2 deciliters per gram, makes it possible to keep the internal viscosity of the polyamide powder composition sufficiently low, even when this composition is obtained by mixing a fresh powder with an already cycled powder used by a PBF powder bed process.

The method for determining the internal viscosity index of plastics and polyamides, according to the ISO 307:2019 standard, is based on the determination of the viscosity index of dilute solutions of polyamides in certain solvents specified in the aforementioned standard.

This viscosity is involved in the rheology of melting and/or coalescence phenomena: the deposited particles must melt and coalesce to form a dense, non-porous mass, but without creeping in an uncontrolled manner. The internal viscosity influences the mechanical properties of the part, its appearance and the surface finish of the finished product.

For optimal use of the powder composition, it is advisable not to exceed a number of recycling cycles for the same powder, that is to say not to recycle again a mixture of powder which has undergone a number high thermal cycling in a PBF powder bed process. The collection of the cycled powder and its sieving must precede the mixing with fresh polyamide powder in order to separate the powder grain aggregates.

The number of possible cycles depends on the degree of oxidation of the recycled powder, knowing that the internal viscosity increases with the degree of oxidation. The inventors note that on average the same powder can be reused in 8 to 10 recycling cycles, but this mainly depends on the duration of exposure of the powder to a high temperature and on the oxygen level in the enclosure, while throughout the thermal cycle undergone (preheating, manufacture at temperature and cooling) either during the entire manufacture in PBF or during cooling to a temperature below 60°C.

Recycling is favored by the fact that the fresh powder has the internal viscosity indicated above. Indeed, to manufacture parts of good quality by the process according to the invention, it is possible to use a powder whose internal viscosity index is located a little outside this zone between 0.9 deciliters per gram and 1.4 deciliters per gram, but so that the fresh powder can be recycled in the PBF process, under advantageous economic conditions and according to the technical conditions indicated above (mixed with fresh powder at a rate of 30% to 60%), it It is preferable to respect, for the fresh powder, a continuous cooling at 50% and the systematic sieving of the already cycled powder.

By way of example, the composition according to the invention is powder A (already described above). Fresh powder A has an internal viscosity index equal to 1.3 deciliters per gram. After implementing a sintering process, a new powder composition according to the invention is formed by mixing half fresh powder and half recycled. After one or two cycles, the powder composition has an equal internal viscosity index of the order of 1.7 deciliters per gram. After three to six cycles, the powder composition has an internal viscosity index of the order of 2.05 deciliters per gram.

[Table 3]

Instead of the number of cycles, the temperature time can be taken into consideration, i.e. the time during which the powder composition is subjected to heating in the heated enclosure. This approach can be more precise because the manufacturing cycles can be longer or shorter. The temperature times tested to arrive at the values of the internal viscosity index in the table above are also indicated. This temperature time is equal to 0 for a fresh powder, it is greater than 20 hours for a powder having undergone 1 to 2 cycles and greater than 50 hours for a powder having undergone 3 to 6 recycling cycles.

Magnetic detection of 3D objects obtained

The presence of an optical or magnetic detection additive in the powder composition of the invention allows the detection of 3D objects obtained by sintering this powder.

In the case of magnetic detection, the 3D objects obtained from a powder comprising a magnetic detection additive are for example detected by electromagnetic induction or according to any other method of detecting a magnetic object. These methods, which are well known to those skilled in the art, are not described here.

Optical detection of 3D objects obtained

3D objects obtained by additive manufacturing of a powder composition are colored in the mass, that is to say that the material constituting the 3D object is colored and that the object does not only present a coloring on its outer surface. This characteristic allows a broken 3D object fragment to present on all its faces the color corresponding to the optical detection additive used. Thus, a fragment of a mass-colored object can be detected by optical detection methods, when the object is broken.

Preferably, the 3D object is colored in blue in the mass. Since the color blue is uncommon among food products, it stands out more easily than other colors when it is in the middle of food products. In particular, infrared detection by irradiation in a wavelength range between 0.5 μm and 12 μm can be implemented. These optical detection methods, even applied to fragments of plastic materials, are well known to those skilled in the art and will not be described here in greater detail.

Mechanical properties of 3D objects obtained by sintering according to the invention

Preferably, a 3D object obtained by sintering according to the invention has a lowest tensile strength greater than or equal to 40 MPa (megapascals), preferably greater than or equal to 44 MPa.

In the case where the 3D object is obtained by sintering a powder comprising a magnetic detection additive, the 4D object preferably has a lowest tensile strength greater than or equal to 30 MPa, very preferably greater than or equal to 35MPa.

Preferably, a 3D object obtained by sintering according to the invention has a lowest modulus of elasticity greater than or equal to 1600 MPa, preferably greater than or equal to 1750 MPa.

In particular, standardized specimens of 3D objects obtained from a sintering process according to the invention were tested for their tensile strength and their modulus of elasticity, expressed in megapascals (MPa) and for their elongation at the rupture, expressed as a percentage. The 3D object tested is obtained from a sintering powder composition A according to the invention comprising an optical detection additive is in which the polyamide is PA11. The test method implemented complies with the ISO 527-1:2019 standard for determining tensile properties.

[Table 4]

Preferably, the 3D objects obtained by the method of the invention have an elongation at break greater than or equal to 20% in a first orientation and greater than or equal to 35% in a second orientation, perpendicular to the first.

In tests conducted according to ISO 527-1:2019, the results of which are shown in Table 4 above, these elongations at break were measured at 25% and 40%.

Figures 10 and 11 show the graphs corresponding to the results of the tests presented above for the elongation at break. In Figure 10 the results of the tensile elongation test along an xy orientation and in Figure 1 1 the results of the tensile elongation test along an xz orientation.

Claims

1. Method for manufacturing a three-dimensional object, comprising a local rise in the temperature of a polyamide-based powder by electromagnetic radiation in a heated enclosure, causing the localized melting of a layer of a predetermined thickness to form , after cooling, a solid layer of polyamide, said method being characterized in that said powder comprises, over the total weight of the composition:

- between 60% and 99% by weight of polyamide;

- between 1% and 40% by weight of an optical and/or magnetic detection additive selected from the group formed by: pigments comprising a spinel structure which contains a cation of a transition metal, oxides of a metal transition, sulfides of a transition metal;

- between 0% and 5% and preferably between 0.1% and 4.5% by weight of a flow agent; and in that the powder has:

- a D ₅₀ particle size distribution of between 35 μm and 55 μm; and

- a D ₁₀ particle size distribution greater than 15 μm and

- a D ₉₀ particle size distribution of less than 100 μm.

2. Method according to claim 1, wherein a mass fraction of between 30% and 70% of said powder is fresh polyamide powder, and a mass fraction of between 70% and 30% of said powder is a polyamide powder recovered from said enclosure heated following a previous manufacture, and in which said fresh polyamide powder has an internal viscosity index measured at 25°C according to ISO 307:2019 of between 0.9 deciliters per gram and 1.4 deciliters per gram.

3. Method according to one of claims 1 or 2, wherein the electromagnetic radiation is laser radiation with an energy density greater than 25 mJ/mm ² .

4. Powder composition for additive manufacturing process by local elevation of the temperature of a polyamide-based powder by electromagnetic radiation in a heated chamber, causing the localized melting of a layer of a predetermined thickness to form, after cooling, a solid layer of polyamide characterized in that the said powder comprises, over the total weight of the composition:

- between 60% and 99% by weight of polyamide

- a D ₅₀ particle size distribution of between 35 μm and 55 μm; and

- a D ₁₀ particle size distribution greater than 15 μm and

- a D ₉₀ particle size distribution of less than 100 μm.

5. Powder composition according to claim 4, which has:

- a D ₅₀ particle size distribution between 35 μm and 55 μm,

- a D ₁₀ particle size distribution of between 15 μm and 25 μm and

- a D ₉₀ particle size distribution of between 80 μm and 100 μm.

6. Powder composition according to one of claims 4 or 5, obtained by dry mixing a natural polyamide powder with a polyamide powder comprising a detection additive.

7. Powder composition according to one of claims 4 to 6, which comprises:

- between 0.05% and 5% by weight of an optical detection additive chosen from pigments comprising a spinel structure which contains a cation of a transition metal and - between 1% and 35% by weight of a magnetic detection additive among the oxides of the transition metals.

8. Powder composition according to one of claims 4 to 7, which has an internal viscosity index measured according to ISO 307:2019 of between 0.9 and 1.4 deciliters per gram, at 25°C.

9. Powder composition according to one of Claims 4 to 8, which has a value ΔT= (T _m -T _c ) _onset., of between 30°C and 50°C.

10. Powder composition according to one of claims 4 to 9, which comprises an optical detection additive and in which said optical detection additive comprises cobalt blue.

11. Three-dimensional object obtained by additive manufacturing from a composition according to one of claims 4 to 10.

12. Object according to claim 11, colored blue in the mass by an optical detection additive and in which said optical detection additive allows optical detection in a wavelength range between 0.5 μm and 12 μm.

13. Object according to one of claims 11 or 12, which has a modulus of elasticity greater than or equal to 1600 MPa, a tensile strength greater than or equal to 30 MPa, an elongation at break greater than or equal to 20% according to a first orientation and greater than or equal to 35% on a second orientation perpendicular to the first.