METHOD FOR PRODUCING 3D PRINTING MATERIAL AND COMPONENTS THEREFROM, AND 3D PRII\TTING MATERIAL AND COMPONENT PRODUCED USING THE METHOD

Abstract

This invention relates to a method for producing 3D printing material. The method involves first producing, from at least one photocatalyst and at least one phyllosilicate, a photocatalyst-phyllosilicate composite; From the photocatalyst-phyllosilicate composite and at least one thermoplastic polymer, a photocatalyst-phyllosilicate-polymer composite is then produced. Finally, the photocatalyst-phyllosilicate-polymer composite is subjected to a shaping process, producing a 3D printing material. This invention also relates to a 3D printing material comprising a thermoplastic matrix and, embedded in the matrix, a composite material containing at least one photocatalyst and at least one phyllosilicate. This invention further relates to a method for producing components from the 3D printing material and a component produced using this method.

Claims

1. A 3D printing material production method comprising: a) producing, from at least one photocatalyst and at least one phyllosilicate, a photocatalyst-phyllosilicate composite; b) producing, from the photocatalyst-phyllosilicate composite and at least one thermoplastic polymer, a photocatalyst-phyllosilicate-polymer composite; and c) subjecting the photocatalyst-phyllosilicate-polymer composite to a shaping process, producing a 3D printing material.

2. The method of claim 1, wherein the at least one photocatalyst: is selected from the group consisting of TiO.sub.2, ZnO, SnO.sub.2, WO.sub.3, Fe.sub.2O.sub.3, Fe.sub.3O.sub.4, MnO, NiO, and mixtures thereof; and/or is doped with at least one metal, or is doped with at least one metal during step a), the at least one metal preferably being selected from the group consisting of Ag, Cu, Au, Pd, Pt, Rh, Cd, and mixtures thereof.

3. The method of claim 1, wherein the at least one phyllosilicate is selected from the group consisting of hectorite, bentonite, montmorillonite, muscovite, illite, kaolinite, halloysite, palygorskite, vermiculite, and mixtures thereof.

4. The method of claim 1, wherein during the production of the photocatalyst-phyllosilicate composite in step a): a weight ratio of the at least one photocatalyst to the at least one phyllosilicate lies in a range from 1:1 to 10:1; and/or the at least one photocatalyst is intercalated into the at least one phyllosilicate and/or is added onto the at least one phyllosilicate.

5. The method of claim 1, wherein during the production of the photocatalyst-phyllosilicate-polymer composite in step b): a weight ratio of the photocatalyst-phyllosilicate composite to the at least one thermoplastic polymer lies in a range from 1:10 to 2:1; and/or the photocatalyst-phyllosilicate composite is compounded with the at least one thermoplastic polymer.

6. The method of claim 1, wherein the at least one thermoplastic polymer is selected from the group consisting of polyamide 6 (PA 6), polyamide 66 (PA 66), polyamide 12 (PA 12), polyamide 4.6 (PA 4.6), acrylonitrile butadiene styrene (ABS), polycarbonates (PC), polyethylene (PE), polypropylene (PP), polyphenylene sulfide (PPS), polyvinyl chloride (PVC), acrylonitrile styrene acrylates, polyurethanes, epoxy resins, and mixtures thereof.

7. The method of claim 1, wherein the shaping process in step c) is selected from the group consisting of extrusion processes, granulation processes, cutting processes, and combinations thereof.

8. A 3D printing material comprising at least one thermoplastic matrix polymer and, embedded in the at least one thermoplastic matrix polymer, a composite material containing at least one photocatalyst and at least one phyllosilicate.

9. The 3D printing material of claim 8, wherein the at least one photocatalyst: is selected from the group consisting of TiO.sub.2, ZnO, SnO.sub.2, WO.sub.3, Fe.sub.2O.sub.3, Fe.sub.3O.sub.4, MnO, NiO, and mixtures thereof; and/or is doped with at least one metal, the at least one metal preferably being selected from the group consisting of Ag, Cu, Au, Pd, Pt, Rh, Cd, and mixtures thereof.

10. The 3D printing material of claim 8, wherein the at least one phyllosilicate; is selected from the group consisting of hectorite, bentonite, montmorillonite, muscovite, illite, kaolinite, halloysite, palygorskite, vermiculite, and mixtures thereof; and/or is in a form of oriented and/or curved lamellae.

11. The 3D printing material of claim 8, wherein the at least one thermoplastic matrix polymer is selected from the group consisting of polyamide 6 (PA 6), polyamide 66 (PA 66), polyamide 12 (PA 12), polyamide 4.6 (PA 4.6), acrylonitrile butadiene styrene (ABS), polycarbonates (PC), polyethylene (PE), polypropylene (PP), polyphenylene sulfide (PPS), polyvinyl chloride (PVC), acrylonitrile styrene acrylates, polyurethanes, epoxy resins, and mixtures thereof.

12. The 3D printing material of claim 8, wherein the 3D printing material contains: 10 to 75 weight %, preferably 20 to 60 weight %, of the at least one thermoplastic matrix polymer, relative to a total weight of the 3D printing material; and/or 10 to 60 weight %, preferably 20 to 50 weight %, of the at least one photocatalyst, relative to the total weight of the 3D printing material; and/or 5 to 40 weight %, preferably 10 to 20 weight %, of the at least one phyllosilicate, relative to the total weight of the 3D printing material.

13. The 3D printing material of claim 8, wherein the 3D printing material is in a form of a granulate, a filament, or rods.

14. The 3D printing material of claim 8, wherein the 3D printing material is produceable or is produced using a method of claim 1.

15. A component production method, comprising: producing 3D printing material according to the method of claim 1; and using 3D printing, preferably an additive fused deposition modeling process, to produce, from the 3D printing material, at least one component.

16. A component comprising: a thermoplastic matrix; and embedded in the thermoplastic matrix, a composite material containing at least one photocatalyst and at least one phyllosilicate, the component being produceable or produced according to the method of claim 15.

Description

[0083] The following figures and examples are intended to explain this invention in detail, without limiting it to the specific embodiments and parameters shown here.

[0084] FIG. 1 is a schematic representation of a sample embodiment of the photocatalyst-phyllosilicate composite produced in step a) of the inventive method. The composite comprises a photocatalyst 1 (e.g., TiO.sub.2 or ZnO), which is doped with a metal 2 (e.g., Cu or Ag); and a phyllosilicate 3 (e.g., hectorite, bentonite, or montmorillonite). The phyllosilicate 3 can be in the form of oriented and/or curved lamellae.

[0085] FIG. 2 is a schematic representation of a sample embodiment of the photocatalyst-phyllosilicate-polymer composite produced in the inventive method. The composite comprises a photocatalyst 1 (e.g., TiO.sub.2 or ZnO), which is doped with a metal 2 (e.g., Cu or Ag); a phyllosilicate 3 (e.g., hectorite, bentonite, or montmorillonite); and a thermoplastic polymer matrix 4. The photocatalyst 1 doped with the metal 2 and the phyllosilicate 3, that is, the photocatalyst-phyllosilicate composite, are embedded in the thermoplastic polymer matrix 4. The phyllosilicate 3 can be in the form of oriented and/or curved lamellae.

SAMPLE EMBODIMENT 1: EFFECT AGAINST BACTERIA

[0086] The first step is to produce a photocatalyst-phyllosilicate composite as follows: 80 mL H.sub.2O are mixed with 20 mL propanol. To this solution is added 1 g of a ca. 40% nanoscale Cu nanoparticle dispersion, and the solution is mixed again. To this mixture are added 5 g of bentonite, and the preparation is then dispersed for 18 h with a magnetic stirrer. After that, 20 g TiO.sub.2 are added, and the resulting mixture is dispersed for one hour. The preparation is dried at 60? C. for 12 h. The preparation is then milled in a powder ball mill for 30 minutes and then calcined at 200? C. for 1 h.

[0087] The second step involves compounding 30 g of the photocatalyst-phyllosilicate composite produced in this way and 30 g of Pebax? (thermoplastic elastomer (TPE-A)) in a co-rotating, 5-zone twin screw compounder at a temperature of T=225? C., to form a granulate.

[0088] The third step involves extruding the granulate through a single screw extruder at a temperature of 205? ? C. to produce FFF filaments having a diameter of 1.75 mm.

[0089] The fourth step involves using FFF printing to print 2.5 cm?2.5 cm test bodies.

[0090] The fifth step is to perform antibacterial tests. To accomplish this, three test samples are loaded with 10.sup.6 CFU/mL of the bacterium Escherichia coli. The first test sample Pebax? catalyst, printed, is provided by a Petri dish, in which is placed one of the test bodies produced in step four. The second test sample Pebax? catalyst, pressed, is provided by a Petri dish, in which is placed a test body that was produced by hot pressing the filaments produced in the third step. The third test sample control sample is a Petri dish without a test body; this test sample is used as a control.

[0091] The three test samples loaded with 10.sup.6 CFU/mL of the bacterium Escherichia coli are irradiated with a light source having the spectrum of sunlight. Before irradiation (0 h), and 1 h and 2 h after irradiation, the bacterial concentration is measured. The measurement is optically determined, the bacteria being counted using a Sorcerer Colony Counter.

[0092] The results of measurements are presented as a diagram in FIG. 3. It can clearly been seen that in the case of the samples Pebax? catalyst, printed and Pebax? catalyst, pressed the bacterial concentration decreases as the irradiation with the light source progresses. After just one hour, the bacterial concentration in both samples has decreased so much that Escherichia coli bacteria are no longer detectable. Even after two hours, no Escherichia coli bacteria were detectable in either sample. By contrast, in the control sample the bacterial concentration remains high, almost unchanged over the entire time.

[0093] Thus, the measurements that were made show an unambiguous reduction in bacteria on the sample Pebax? catalyst, printed and on the sample Pebax? catalyst, pressed during irradiation with light.

[0094] This result is also illustrated by FIG. 4, which shows photographs of the test samples before irradiation (0 h), and 1 h and 2 h after irradiation. It can be seen that after 1 hour there has already been a clear reduction in the bacteria on the test surfaces of the sample Pebax? catalyst, printed and the test sample Pebax? catalyst, pressed.

SECOND SAMPLE EMBODIMENT: EFFECT AGAINST VIRUSES

[0095] The first step is to produce a photocatalyst-phyllosilicate composite as follows: 80 mL H.sub.2O are mixed with 20 mL propanol. To this solution is added 1 g of a ca. 40% nanoscale Cu nanoparticle dispersion, and the solution is mixed again. To this mixture are added 5 g of bentonite, and the preparation is then dispersed for 18 h with a magnetic stirrer. After that, 20 g TiO.sub.2 are added, and the resulting mixture is dispersed for one hour. The preparation is dried at 60? C. for 12 h. The preparation is then milled in a powder ball mill for 30 minutes and then calcined at 200? ? C. for 1 h.

[0096] The second step involves compounding 30 g of the photocatalyst-phyllosilicate composite produced in this way and 30 g of Pebax? (thermoplastic elastomer (TPE-A)) in a co-rotating, 5-zone twin screw compounder at a temperature of T=225? C., to form a granulate.

[0097] The third step involves extruding the granulate through a single screw extruder at a temperature of 205? ? C. to produce FFF filaments having a diameter of 1.75 mm.

[0098] The fourth step involves using FFF printing to print 5 cm?5 cm test bodies.

[0099] The fifth step is to perform antiviral tests. To accomplish this, four test samples are produced by taking four of the test bodies produced in step four, which have a geometry of 5 cm?5 cm, and loading them with 108 viruses/mL of the herpesvirus pseudorabies virus (PVR).

[0100] Two of the loaded test samples are irradiated with a light source having the spectrum of sunlight, and two others are shaded.

[0101] All four samples are dried to the so-called desiccation point (DP).

[0102] One of the two samples irradiated with the light source and one of the two shaded samples are coated with a cell culture directly after drying. The two other samples are coated with a cell culture only 30 minutes after drying. Coating with the cell culture involves placing 1,000 ?L of nutrient medium Dulbecco's modified Eagle's medium (DMEM) and PK-15 cell cultures on the samples.

[0103] After 72 hours the concentration of infected cells is optically determined, to determine the TCID50 (Median Tissue Culture Infectious Dose) value. The measurement is made by an optical determination that involves counting the cells with a Sorcerer Colony Counter.

[0104] The results of the measurements are presented in the form of a diagram in FIG. 5. It can clearly be seen that the viral concentration decreases after irradiation with the light source. Thus, the two irradiated samples have a clearly lower viral concentration than the two shaded samples. In the case of the sample that was irradiated with the light source and that was coated with the cell culture only 30 minutes later (that is, 30 minutes after drying), no viruses or damaged cells are detectable. By contrast, in the case of the shaded samples, the viral concentration remains almost unchanged over the same time. Thus, it is clearly demonstrated that the virus breakdown is caused by the irradiation with the light source and not merely by the drying and waiting time.

[0105] In addition, FIG. 6 shows sections of microscopic pictures obtained during measurement and used during counting. In the left part (A), a section is shown of microscopic picture of the sample that was irradiated with light and coated with the cell culture 30 minutes after drying. This sample is free of viruses and has living cells. In the right part (B), a section is shown of microscopic picture of the sample that was shaded and coated with the cell culture 30 minutes after drying. This sample has infected cells and cells killed by the virus (round spots).

[0106] Thus, the measurements that were made prove unambiguous destruction of viruses during irradiation by light.