CN113619103A - Flame-retardant three-dimensional molded article and method for producing same - Google Patents
Flame-retardant three-dimensional molded article and method for producing same Download PDFInfo
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- CN113619103A CN113619103A CN202010382398.5A CN202010382398A CN113619103A CN 113619103 A CN113619103 A CN 113619103A CN 202010382398 A CN202010382398 A CN 202010382398A CN 113619103 A CN113619103 A CN 113619103A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 113
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000002791 soaking Methods 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000011148 porous material Substances 0.000 claims description 42
- 239000000843 powder Substances 0.000 claims description 24
- 238000000465 moulding Methods 0.000 claims description 14
- 230000004927 fusion Effects 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
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- 239000000243 solution Substances 0.000 description 34
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- 238000013461 design Methods 0.000 description 9
- 238000005245 sintering Methods 0.000 description 9
- 239000000654 additive Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- 238000003475 lamination Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 150000002896 organic halogen compounds Chemical class 0.000 description 4
- 150000002903 organophosphorus compounds Chemical class 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
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- 238000012545 processing Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000012958 reprocessing Methods 0.000 description 3
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- 229940058344 antitrematodals organophosphorous compound Drugs 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
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- 229920000768 polyamine Polymers 0.000 description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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Images
Classifications
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- 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
- B29C64/00—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
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
-
- 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
- B29C64/00—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
- B29C64/30—Auxiliary operations or equipment
- B29C64/379—Handling of additively manufactured objects, e.g. using robots
-
- 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
- B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
- B29C71/0009—After-treatment of articles without altering their shape; Apparatus therefor using liquids, e.g. solvents, swelling agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
- B33Y40/20—Post-treatment, e.g. curing, coating or polishing
-
- 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
- B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
- B29C71/0009—After-treatment of articles without altering their shape; Apparatus therefor using liquids, e.g. solvents, swelling agents
- B29C2071/0018—Absorbing ingredients, e.g. drugs, flavourings, UV screeners, embedded in the articles
-
- 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
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
- B29K2105/0026—Flame proofing or flame retarding agents
-
- 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
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
- B29K2105/045—Condition, form or state of moulded material or of the material to be shaped cellular or porous with open cells
Abstract
The present application relates to a three-dimensional shaped article having flame retardancy and a method for manufacturing the same. The manufacturing method comprises the following steps: a) providing a body, wherein the body comprises a plurality of first holes and a plurality of second holes, the first holes are communicated inwards from the outer surface of the body, the first holes are at least partially communicated with the second holes, and the first average hole width of the first holes is larger than the second average hole width of the second holes; b) soaking the body in a flame retardant solution, and maintaining the body in a negative pressure environment for a soaking time so that the flame retardant solution is soaked in the first holes and the second holes, wherein the flame retardant solution is composed of a flame retardant and a solvent; and c) removing the solvent in the first holes and the second holes to obtain the flame-retardant three-dimensional molded object.
Description
Technical Field
The present application relates to three-dimensional molding, and more particularly, to a flame retardant three-dimensional molded article and a method of manufacturing the same.
Background
In recent years, three-dimensional molding techniques such as Additive Manufacturing (Additive Manufacturing) have been greatly improved, and due to the great increase in speed, industrial production can be realized and the three-dimensional molding techniques are applied to general products. Only limited by the three-dimensional forming process and the limitation of the types of raw materials, the method cannot fully replace the die product or achieve the goal of mass production. Especially on the flame-retardant grade of the product, the three-dimensional forming object is more difficult to break through the limitation of raw materials. The three-dimensional molded articles currently available on the market can only meet the UL94-HB rating in the Standard for Safety of Flammability of Plastic Materials, and most of them can not reach the UL94-V0 rating and the UL94-5VA rating. If the material with high flame-retardant grade is used for three-dimensional molding, although the flame-retardant property can be improved, the expensive material and the manufacturing cost are increased, and the competitiveness of the product cannot be improved.
Therefore, how to develop a flame-retardant three-dimensional shaped article and a method for manufacturing the same to solve the problems of the prior art are the problems to be solved in the art.
Disclosure of Invention
The object of the present application is to provide a flame-retardant three-dimensional shaped article and a method for producing the same. The pore ratio including the first average pore width and the second average pore width is formed by the pore variation generated by the material stack in the lamination manufacturing (additive manufacturing), for example, so as to form a sufficient specific surface area, which is beneficial for the subsequent flame retardant to be evenly dispersed in the pores of the three-dimensional shaped object by, for example, soaking, and form the flame-retardant three-dimensional shaped object. The first average pore width and the second average pore width can be controlled by adjusting the size of raw materials, sintering energy and process parameters, and can also be controlled by structural design, so that the efficiency of introducing a flame retardant into a three-dimensional formed object is increased, the manufacturing process is shortened, and the flame retardance of the three-dimensional formed object is improved.
It is another object of the present application to provide a three-dimensional shaped article having flame retardancy and a method for manufacturing the same. The size of the huge holes in the three-dimensional formed object is controlled by means of structural design and the size of the medium-sized holes in the three-dimensional formed object is controlled by means of lamination manufacturing parameters, so that the three-dimensional formed object is formed to contain the huge and medium-sized holes, the flame retardant is favorably soaked into the holes in a liquid state and uniformly dispersed in the three-dimensional formed object, and the manufacture of the flame-retardant three-dimensional formed object is realized. The structure of the large holes is helpful for accelerating the introduction of the flame retardant into the holes, and the structure of the medium holes is helpful for increasing the uniformity of the distribution of the flame retardant. Therefore, the flame-retardant three-dimensional shaped object can realize the optimized process.
It is still another object of the present application to provide a three-dimensional shaped article having flame retardancy and a method for manufacturing the same. Because the three-dimensional forming object is added with the flame retardant after the lamination manufacturing forming, the flame retardant is prevented from influencing the dimensional precision variation or the structure processing, and the raw material recovery and the reprocessing of the three-dimensional forming object are facilitated.
To achieve the foregoing object, the present application provides a method of manufacturing a three-dimensional shaped article having flame retardancy. The manufacturing method comprises the following steps: a) providing a body, wherein the body comprises a plurality of first holes and a plurality of second holes, wherein the plurality of first holes are communicated inwards from at least one outer surface of the body, the plurality of first holes and the plurality of second holes are at least partially communicated with each other, the plurality of first holes have a first average hole width, and the plurality of second holes have a second average hole width, wherein the first average hole width is greater than the second average hole width; b) soaking the body in a flame retardant solution, and maintaining the body in a negative pressure environment for a soaking time so that the flame retardant solution is soaked in the first holes and the second holes, wherein the flame retardant solution is composed of a flame retardant and a solvent; and c) removing the solvent in the first holes and the second holes to obtain the flame-retardant three-dimensional molded object.
In one embodiment, the first average pore width is between 50 microns and 100 microns, and the second average pore width is between 2 microns and 50 microns.
In one embodiment, the body is formed by a powder bed (powder bed) fusion molding technique.
In one embodiment, the total surface area formed by the inner surfaces of the second plurality of holes is greater than the total surface area formed by the inner surfaces of the first plurality of holes.
In one embodiment, the body is made of polydodecalactam powder, and the average particle size of the polydodecalactam powder ranges from 10 micrometers to 70 micrometers.
In one embodiment, the specific surface area of the first holes and the second holes of the body ranges from 0.2 square meter/gram to 1.0 square meter/gram.
In one embodiment, the negative pressure environment has a negative pressure greater than 50 kilopascals (kPa) and the soaking time is between 1 minute and 10 minutes.
To achieve the above object, the present application further provides a flame-retardant three-dimensional molded article, which includes a body and a flame retardant. The body includes a plurality of first holes and a plurality of second holes, wherein the plurality of first holes are from at least an surface of body intercommunication inwards, and a plurality of first holes and a plurality of second holes at least partially communicate each other, and a plurality of first holes have a first average hole width, and a plurality of second holes have a second average hole width, and wherein first average hole width is greater than second average hole width. The fire retardant is distributed in the first holes and the second holes.
In one embodiment, the first average pore width is between 50 microns and 100 microns, and the second average pore width is between 2 microns and 50 microns.
In one embodiment, the body is formed by a powder bed fusion molding technique.
In one embodiment, the total surface area formed by the inner surfaces of the second plurality of holes is greater than the total surface area formed by the inner surfaces of the first plurality of holes.
In one embodiment, the body is made of polydodecalactam powder, and the average particle size of the polydodecalactam powder ranges from 10 micrometers to 70 micrometers.
In one embodiment, the specific surface area of the first holes and the second holes ranges from 0.2 square meter/gram to 1 square meter/gram.
Drawings
FIG. 1 is a flow chart showing a method for manufacturing a flame-retardant three-dimensional molded article according to a preferred embodiment of the present application.
FIG. 2 is a schematic view showing the appearance and structure of a three-dimensional shaped article having flame retardancy according to a preferred embodiment of the present application.
FIG. 3 is a schematic view showing the microstructure of a three-dimensional shaped article having flame retardancy according to a preferred embodiment of the present application.
Fig. 4A to 4D are schematic views showing the structure of stages of the method for manufacturing a three-dimensional shaped article having flame retardancy according to the preferred embodiment of the present application.
List of reference numerals
1: three-dimensional shaped article having flame retardancy
10: body
11: a first hole
12: second hole
13: flame retardant
13 a: flame retardant solution
W1: first average hole width
W2: second average hole width
S0: outer surface
S1: inner surface
S2: inner surface
S01-S03: step (ii) of
Detailed Description
Some exemplary embodiments that embody features and advantages of the present application will be described in detail in the description that follows. It should be understood that the present application is capable of many variations in form and arrangement without departing from the scope of the application, and that the description and drawings herein are to be regarded as illustrative in nature and not as restrictive.
FIG. 1 is a flow chart showing a method for manufacturing a flame-retardant three-dimensional molded article according to a preferred embodiment of the present application. FIG. 2 is a schematic view showing the appearance and structure of a three-dimensional shaped article having flame retardancy according to a preferred embodiment of the present application. FIG. 3 is a schematic view showing the microstructure of a three-dimensional shaped article having flame retardancy according to a preferred embodiment of the present application. Fig. 4A to 4D are schematic views showing the structure of stages of the method for manufacturing a three-dimensional shaped article having flame retardancy according to the preferred embodiment of the present application. In this embodiment, the three-dimensional shaped article 1 having flame retardancy is manufactured in stages. First, in step S01, a body 10 is first formed by a technique such as, but not limited to, Powder Bed Fusion (PBF), and the body 10 is provided with a plurality of first holes 11 and a plurality of second holes 12. The first holes 11 are connected inward from at least one outer surface S0 of the body 10, and the first holes 11 and the second holes 12 are connected at least partially to each other, the first holes having a first average hole width W1, and the second holes 12 having a second average hole width W2. Wherein the first average hole width W1 is greater than the second average hole width W2. Next, in step S02, the main body 10 is soaked in a fire retardant solution 13a in a vacuum impregnation apparatus, and is maintained in a negative pressure environment for a soaking time, so that the fire retardant solution 13a is soaked in the first holes 11 and the second holes 12. The flame retardant solution 13a is composed of a flame retardant 13 and a solvent (not shown). In this embodiment, the flame retardant may be, for example, a powder type flame retardant selected from the group consisting of Minerals (Minerals), Organic halogen compounds (Organohalogen compounds), Organic phosphorus compounds (organophosphorous compounds) and Organic compounds (Organic compounds). In the present embodiment, the solvent may be, for example, an organic solvent or water, and any substance that can dissolve the flame retardant 13 to form the flame retardant solution 13a is suitable for the present application. When the fire retardant solution 13a is maintained in the negative pressure environment for, for example, less than 10 minutes, the fire retardant solution 13a is soaked into the first holes 11 and the second holes 12. In the embodiment, the negative pressure value of the negative pressure environment is greater than 50 kilopascal (kPa), and the soaking time is between 1 minute and 10 minutes, so that the flame retardant solution 13a can completely fill the first holes 11 and the second holes 12. More preferably, when the negative pressure value of the negative pressure environment is 75 kilopascal (kPa), the soaking time is 1 to 3 minutes, so that the flame retardant solution 13a can be completely soaked into the first holes 11 and the second holes 12, as shown in fig. 4B. After the body 10 soaked with the flame retardant solution 13a is moved out of the vacuum impregnation equipment, the flame retardant solution 13a is still attached to the inner surfaces S1 of the first holes 11 and the inner surfaces S2 of the second holes 12. The flame retardant solution 13a also remains completely filled in the plurality of second holes 12, as shown in fig. 4C. Finally, the body 10 soaked in the flame retardant solution 13a is dried to remove the solvent in the first holes 11 and the second holes 12, so that the flame retardant 13 is attached to the inner surfaces S1 of the first holes 11 and the inner surfaces S2 of the second holes 12, and the flame retardant three-dimensional molded article 1 can be obtained.
It is noted that the present application forms the body 10 with a porosity of the first average pore width W1 and the second average pore width W2, such as the porosity of the material stack in additive manufacturing, to have a sufficient specific surface area in the range of 0.2 square meters per gram (m)2Per gram) to 1.0 square meter per gram (m)2Is/g). Wherein the first average hole width W1 is more than a multiple of the second average hole width W2. In the present embodiment, the first average hole width W1 and the second average hole width W2 can be controlled by adjusting, for example, the raw material size, sintering energy and process parameters, or by the structure design. When the body 10 is formed by a powder bed fusion molding (PBF) technique, the first holes 11 can be, for example, giant holes formed by a manufacturing process, and the second holes 12 can be, for example, medium holes formed by a manufacturing process. In one embodiment, the first average hole width W1 of the first hole 11 is greater than 50 micrometers (μm), and the second average hole width W2 of the second hole 12 is less than 50 micrometers (μm). In other embodiments, the first average hole width W1 is between 50 micrometers (μm) and 100 micrometers (μm), and the second average hole width W2 is between 2 micrometers (μm) and 50 micrometers (μm). Of course, in other embodiments, the first holes 11 of the body 10 further include macro holes larger than 100 micrometers (μm), and the second holes 12 further include micro holes smaller than 2 micrometers (μm), which is not limited herein.
Taking polydodecalactam (Polyamide 12, PA12) powder used in a powder bed melt molding (PBF) technique as an example, the average particle size of the polydodecalactam powder ranges from 10 to 70 microns, preferably 60 microns. By controlling the size of the giant pores in the body 10 through the structural design (design of appearance structure) and controlling the size of the medium pores in the body 10 through the additive manufacturing parameters (such as the size of raw material and the size of sintering energy), the body 10 can comprise a first average pore width W1 of 50-100 micrometers and a second average pore width W2 of 2-50 micrometers. In other words, the present application controls the size of the giant pores in the three-dimensional molded object 1 and the size of the medium pores in the three-dimensional molded object 1 by means of the structural design and the additive manufacturing parameters, so that the body 10 of the three-dimensional molded object 1 is formed to include, for example, the giant and medium first pores 11 and the medium second pores 12, so as to facilitate the flame retardant 13 to be soaked into the first pores 11 and the second pores 12 in the liquid state of the flame retardant solution 13a and uniformly dispersed in the body 10, thereby realizing the manufacture of the three-dimensional molded object 1 with flame retardancy. Wherein the first holes 11 such as the giant holes help to accelerate the introduction of the flame retardant solution 13a containing the flame retardant 13, and the second holes 12 of the medium-sized holes help to increase the uniformity of the distribution of the flame retardant 13. In one example, the total surface area formed by the inner surfaces S2 of the second holes 12 is larger than the total surface area formed by the inner surfaces S1 of the first holes. Of course, the number, size and distribution of the first holes 11 and the second holes 12 can be adjusted and varied according to the practical application, for example, different flame retardants 13 can be added according to the requirements of different flame retardant grades. This application is through the hole porosity of adjustment body 10, does benefit to the efficiency that increases the leading-in body 10 of fire retardant 13, shortens the manufacturing procedure, promotes the fire resistance of three-dimensional shaping article 1, realizes the optimization technology.
On the other hand, in the present embodiment, the flame retardant 13 may be, for example, a powder type flame retardant selected from the group consisting of Minerals (Minerals), Organic halogen compounds (Organohalogen compounds), Organic phosphorus compounds (organophosphorous compounds) and Organic compounds (Organic compounds), and the solvent may be, for example, any substance that can dissolve the flame retardant 13 to form the flame retardant solution 13 a. It should be noted that, besides being influenced by the number, size and distribution of the first holes 11 and the second holes 12, the impregnation effect of the flame retardant solution 13a may be different solution systems according to the hydrophilicity or lipophilicity of the material of the body 10. In the present embodiment, the main body 10 of the three-dimensional molded object 1 is made of polydodecalactam (Polyamide 12, PA12) powder, and the surface of the polydodecalactam polymer is preferably made of the flame retardant solution 13a formed by an organic solvent system because the proportion of hydrophilic groups of amide groups is low. In other embodiments, the fire retardant solution 13a may be an aqueous solution system, and a surfactant may also be added to increase the compatibility between the fire retardant solution 13a and the inner surfaces S1 of the first hole 11 and the inner surfaces S2 of the second hole 12, so as to achieve better wettability and improve the impregnation effect of the fire retardant solution 13 a. Of course, the present application is not limited thereto.
Refer to fig. 1 to 3 and fig. 4A to 4D. In a first example, poly-dodecalactam (polyamine 12, PA12) powder was subjected to powder bed melt forming (PBF) with low sintering energy to produce a first test piece with a thickness of 3.0 millimeters (mm). Wherein the first average pore width W1 of the first pores 11 is designed to be about 100 micrometers (μm), the second average pore width W2 of the second pores 12 with high porosity obtained by low sintering energy is about 2 micrometers (μm), and the specific surface area of the body 10 of the test piece I is 0.8727 square meters per gram (m is m)2In terms of/g). The first test piece is immersed in a flame retardant solution 13a composed of a powdery flame retardant 13 and Methyl Ethyl Ketone (MEK). The first test piece is soaked in the flame retardant solution 13a for 5 minutes by vacuum impregnation equipment, and the negative pressure value of the negative pressure environment is controlled to be 75 kilo (kPa), so that the flame retardant solution 13a is soaked into the first hole 11 and the second hole 12. And (5) reducing the pressure after the vacuum soaking is finished. And drying the first test piece by using a drying device, drying the first test piece at 50 ℃ for 10 minutes, and removing the solvent in the flame retardant solution 13a to leave the flame retardant 13 in the first hole 11 and the second hole 12. The test piece obtained, once tested for the Flammability Safety of Plastic Materials (Safety of flame of Plastic Materials), stops burning within 30 seconds, meeting the UL94-V2 rating.
In addition, in a first stepIn the second example, polydodecalactam (polyamine 12, PA12) powder was subjected to powder bed melt molding (PBF) at high sintering energy to prepare test piece two having a thickness of 3.0 millimeters (mm). Wherein the first average pore width W1 of the first pores 11 is about 100 micrometers (μm), the second average pore width W2 of the low porosity second pores 12 obtained by high sintering energy is about 10 micrometers (μm), and the specific surface area of the body 10 of the second test piece is 0.2947 square meters per gram (m)2In terms of/g). The test piece two was immersed in a flame retardant solution 13a composed of a powdery flame retardant 13 and Methyl Ethyl Ketone (MEK). The first test piece is soaked in the flame retardant solution 13a for 5 minutes by vacuum impregnation equipment, and the negative pressure value of the negative pressure environment is controlled to be 75 kilo (kPa), so that the flame retardant solution 13a is soaked into the first hole 11 and the second hole 12. And (5) reducing the pressure after the vacuum soaking is finished. And drying the second test piece by using a drying device, drying the second test piece at 50 ℃ for 10 minutes, and removing the solvent in the flame retardant solution 13a to leave the flame retardant 13 in the first hole 11 and the second hole 12. The obtained test piece II is subjected to a plastic material flammability safety test, and the test piece II vertically arranged above the flame stops burning within 30 seconds, so that the test piece II can meet the UL94-V2 rating.
It should be noted that the variation of the holes formed in the lamination manufacturing of the present application can form a sufficient specific surface area, and the subsequent flame retardant 13 is effectively dispersed in the holes to form the flame-retardant three-dimensional molded article 1. The shape of the holes is controlled by adjusting the structural design, the size of raw materials, the sintering energy and the process parameters, so that the efficiency of introducing the flame retardant into the three-dimensional formed object is increased, the manufacturing process is shortened, and the flame retardance of the three-dimensional formed object 1 is improved. The flame retardant 13 is uniformly distributed in the body 10 through the first holes 11 and the second holes 12, rather than being coated on the surface of the body 10, and the flame retardant effect achieved is equivalent to that of a product produced by using an expensive burning-resistant material, but the material cost and the production cost can be lower, so that the three-dimensional molded object 1 with flame retardancy has higher industrial competitiveness.
On the other hand, since the flame-retardant three-dimensional molded article 1 of the present invention is formed by adding the flame retardant 13 after the molded body 10 is laminated, it is possible to prevent the flame retardant 13 from affecting the dimensional accuracy variation or the structural processing process in the molding process. Before the flame retardant 13 is added, the body 10 is made of a simple material, so that the recovery and reprocessing of the raw materials of the molded body 10 are facilitated, and the physical or chemical characteristics of the recovered raw materials are not influenced. The flame retardant solution 13a does not affect the overall appearance, material or original process of molding when applied to the body 10 formed by powder bed melt molding (PBF) techniques. The same laminated material can be manufactured by adjusting the number, size and distribution of the first holes 11 and the second holes 12 or the addition amount of the flame retardant 13 according to the practical application requirements, so as to achieve different flame resistance requirements. Of course, the present application is not limited to the types of the materials and the flame retardant 13 for the additive manufacturing, and the description thereof is omitted.
In summary, the present application provides a three-dimensional shaped article having flame retardancy and a method of manufacturing the same. The pore ratio including the first average pore width and the second average pore width is formed by the pore change generated by the material stacking in the lamination manufacturing, for example, so as to form a sufficient specific surface area, so that the subsequent flame retardant is uniformly dispersed in the pores of the three-dimensional formed object by, for example, soaking, and the three-dimensional formed object with flame retardance is formed. The first average pore width and the second average pore width can be controlled by adjusting the size of raw materials, sintering energy and process parameters, and can also be controlled by structural design, so that the efficiency of introducing a flame retardant into a three-dimensional formed object is increased, the manufacturing process is shortened, and the flame retardance of the three-dimensional formed object is improved. In addition, the size of the huge holes in the three-dimensional forming object is controlled by means of structural design and the size of the medium-sized holes in the three-dimensional forming object is controlled by means of lamination manufacturing parameters, so that the three-dimensional forming object is formed to contain the huge and medium-sized holes, the flame retardant can be conveniently soaked into the holes in a liquid state and uniformly dispersed in the three-dimensional forming object, and the manufacturing of the flame-retardant three-dimensional forming object is achieved. The structure of the large holes is helpful for accelerating the introduction of the flame retardant into the holes, and the structure of the medium holes is helpful for increasing the uniformity of the distribution of the flame retardant. Therefore, the flame-retardant three-dimensional shaped object can realize the optimized process. On the other hand, the three-dimensional forming object is added with the flame retardant after lamination manufacturing and forming, so that the influence of the flame retardant on dimensional precision variation or structural processing is avoided, and the raw material recovery and reprocessing of the three-dimensional forming object are facilitated.
The present application is capable of numerous modifications as may be devised by those skilled in the art, without departing from the scope of the appended claims.
Claims (13)
1. A method for manufacturing a three-dimensional shaped article having flame retardancy, comprising the steps of:
a) providing a body, wherein the body comprises a plurality of first cavities and a plurality of second cavities, wherein the plurality of first cavities are in communication from at least one outer surface of the body, and the plurality of first cavities and the plurality of second cavities are in at least partial communication with each other, the plurality of first cavities having a first average cavity width, and the plurality of second cavities having a second average cavity width, wherein the first average cavity width is greater than the second average cavity width;
b) soaking the body in a flame retardant solution, and maintaining the body in a negative pressure environment for a soaking time so that the flame retardant solution is soaked in the first holes and the second holes, wherein the flame retardant solution is composed of a flame retardant and a solvent; and
c) and removing the solvent in the first holes and the second holes to obtain the flame-retardant three-dimensional molded object.
2. The method of claim 1, wherein the first average pore width is between 50 microns and 100 microns and the second average pore width is between 2 microns and 50 microns.
3. The method of claim 1, wherein the body is formed by a powder bed fusion molding technique.
4. The method of manufacturing according to claim 3, wherein the inner surfaces of the second plurality of cavities form a larger total surface area than the inner surfaces of the first plurality of cavities.
5. The method of claim 3, wherein the body is made of polydodecalactam powder having an average particle size ranging from 10 to 70 μm.
6. The method of claim 5, wherein the specific surface area of the body ranges from 0.2 m/g to 1.0 m/g.
7. The method of claim 5, wherein the sub-atmospheric pressure is greater than 50 kilopascals (kPa) and the soaking time is between 1 minute and 10 minutes.
8. A three-dimensional shaped article having flame retardancy, comprising:
a body comprising a plurality of first voids and a plurality of second voids, wherein the plurality of first voids are in communication from at least an outer surface of the body inward, and the plurality of first voids and the plurality of second voids are in at least partial communication with each other, the plurality of first voids having a first average void width, and the plurality of second voids having a second average void width, wherein the first average void width is greater than the second average void width; and
and the fire retardant is distributed in the first holes and the second holes.
9. The flame retardant, three-dimensional shaped article according to claim 8, wherein the first average pore width is between 50 microns and 100 microns and the second average pore width is between 2 microns and 50 microns.
10. The three-dimensional shaped flame retardant article according to claim 8, wherein the body is formed by a powder bed melt molding technique.
11. The three-dimensional shaped article having flame retardancy according to claim 10, wherein the inner surfaces of the plurality of second cavities form a larger total surface area than the inner surfaces of the plurality of first cavities.
12. The three-dimensional shaped flame-retardant article according to claim 10, wherein the body is made of polydodecalactam powder, and the mean particle size of the polydodecalactam powder is in the range of 10 to 70 μm.
13. The three-dimensional shaped flame-retardant article according to claim 12, wherein the specific surface area of the body ranges from 0.2 m/g to 1 m/g.
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