Composition for three-dimensional printing, a method for preparation thereof and uses thereof

Abstract

The disclosure concerns a composition for three-dimensional printing, said composition being free from polylactic acid (PLA) and includes the following components: (a) a polysaccharide comprising a cellulose derivative and/or a lignocellulosic derivative; (b) a pH regulator selected from at least one of the following: organic acids, inorganic acids, acid generating salts, bases, buffers, (c) a resin selected from melamine resin and/or phenol resin, and (d) optionally a rheology modifier selected from water and/or glycerol. The disclosure also concerns a kit of parts for producing the described composition, a method for three-dimensional printing of the described composition and articles obtainable by said method.

Claims

1. A kit of parts for providing a composition in the form of a paste for three-dimensional printing, said composition being free from polylactic acid and comprising the following components: (a) a polysaccharide comprising a cellulose derivative and/or a lignocellulosic derivative selected from at least one of the following: a wood fiber, sander dust, sawing dust, a lignocellulosic fiber, a lignocellulosic paste, a lignocellulosic powder, a cellulose powder, a cellulose paste, a cellulose fiber, a regenerated cellulose, and a lignocellulosic composite; (b) a pH regulator selected from at least one of the following: an organic acid, an inorganic acid, an acid generating salt, a buffer, an acidic polymer, and a base; (c) a resin selected from a melamine resin and/or a phenol resin; (d) a rheology modifier selected from water and/or glycerol; and (f) an organic filler selected from at least one of the following: a cellulose fiber, algenite, cork, latex, wax, shellac, and gum arabic; wherein said kit of parts comprises: (i) a first component comprising said pH regulator; and (ii) a second component comprising said resin, wherein said first component and/or said second component further comprise(s) said polysaccharide; wherein said first component and said second component further comprise said rheology modifier thereby providing said first component as a paste and said second component as a second paste; and wherein said first component and/or said second component further comprise(s) said organic filler.

2. A kit according to claim 1, wherein the resin comprises melamine urea formaldehyde and/or melamine formaldehyde.

3. A kit according to claim 1, wherein said first and/or said second component further comprise at least one of the following components: (e) a binder selected from at least one of the following: starch, lignin, and a protein, (g) a functionality carrier selected from at least one of the following: metallic particles, carbon, glass particles, and caprolactam, and (h) a further rheology modifier selected from at least one of the following: an acrylic polymer, an alginate, a gum derived from cellulose, and a cellulose fiber.

4. A kit according to claim 1, wherein the amount of the components based on the total amount of the composition is: from 10 wt % to 87 wt % of the polysaccharide comprising a cellulose derivative and/or lignocellulose derivative, from 0.1 wt % to 10 wt % of the pH regulator, from 5 wt % to 70 wt % of the resin and a binder selected from at least one of the following: starch, lignin, and a protein, from 1 wt % to 10 wt % of the organic filler, 0.1 to 10 wt % of a functionality carrier selected from at least one of the following: metallic particles, carbon, glass particles, and caprolactam, water, glycerol and/or binder present in an amount up to 100 wt % of the balance of the composition.

5. A kit according to claim 1, wherein said composition is biodegradable.

6. A kit according to claim 1, wherein said composition is capable of three-dimensional printing at room temperature.

7. A kit according to claim 1, wherein said composition is capable of three-dimensional printing without heating and/or cooling.

Description

EXAMPLES

(1) Materials

(2) Preparation of Materials for 3D Printing.

(3) List of Material:

(4) TABLE-US-00001 Name Suppliers Specification Kaolin BASF AVG. PARTICLE SIZE 2.5 μm-5 μm Arbocel J. Rettenmeier Wood meal & Söne GmbH MAX PARTICLE SIZE 80 μm Corn starch Cargill AVG. PARTICLE SIZE 20 μm Sander dust European MDF MAX PARTICLE SIZE plant 150 μm Sodium Algenate Sigma Aldrich CAS Number: 9005-38-3 Prefere ExpL-3089 Dynea melamine urea resin containing more than 20 wt % melamine and having a molar ratio formalde- hyde:amino groups of 0.9:1 or less Micronised wax Lubrizol Melting point >100° C. Formic acid — 85 wt % in water Oxalic acid — Powder Glycerol Sigma Aldrich 86 wt % in water Elotex Akzo-Nobel — Caprolactam — — Wood fibres MDF plant — Cellulose Fibres 10% paste

(5) In this document wt % refers to % by weight based in the total weight.

Example 1

(6) Water (71.1 g), glycerol (13.4 g), formic acid (65.9 g), were mixed by Rodelys RS 300 stirrer at 250 rpm. Corn starch (184.7 g), kaolin (164.7 g) were added slowly (over 30 min) and simultaneously into the mix under stirring of 180 rpm to provide a first homogenous paste composition. In this document, rpm intends revolutions per minute.

(7) Water (87.5 g) was added to Prefere ExpL-3089 (312 g) synthetic binder from Dynea under stirring of 300 rpm). Micronised wax (2.5 g) and Arbocel (43.3 g) were stirred in the mix, at 130 rpm to provide a second homogenous paste composition.

Example 2

(8) Water (104 g), oxalic acid (29 g), were mixed by Rodelys RS 300 stirrer at 250 rpm. Wood fibres (150), sander dust (97.7 g) were added slowly (over 30 min) and simultaneously into the mix under stirring of 180 rpm to provide a first homogenous paste composition.

(9) Water (100 g) was added to Prefere ExpL-3089 (170 g) under stirring of 300 rpm. Caprolactam (2 g) and Arbocel (89.5 g) were stirred in the mix, at 130 rpm. Corn starch (37 g) was added to provide a second homogenous paste composition.

Example 3

(10) Water (60 g), formic acid (15 g), were mixed by Rodelys RS 300 stirrer at 250 rpm. Arbocel (130 g) and kaolin (130 g) were added slowly (over 30 min) and simultaneously into the mix under stirring of 180 rpm to provide a first homogenous paste composition.

(11) Water (100 g) was added Prefere ExpL-3089 (100 g) under stirring of 300 rpm and cellulose fibres (10 g) were added. Elotex (95 g) and Arbocel (130 g) were stirred in the mix, at 130 rpm to provide a second homogenous paste composition.

Example 4

(12) Sander dust (320 g) was mixed with wood-fibres (64 g), corn starch (31 g) Prefere ExpL-3089 (120 g) and ammonium sulphate (14 g) to form a powder mixture for 3D printing.

(13) Printing/Extruding Procedure

(14) The pastes of Examples 1-3 were tested for three-dimensional printing as follows.

(15) The first homogenous paste and the second homogenous paste were mixed in 50:50 (w/w) ratio in inline mixer at pressure of 2-5.5 bar, through a nozzle of 0.5-6 mm to be extruded into objects.

(16) Objects with layer height from 2-7 mm and layer width of 2-7 mm, at speed of 3.5 s/cm were extruded. The layers were dried just after extrusion.

(17) The dried objects were immersed into cold for 24 h and warm water (60° C.) for 4 hours.

(18) There was no change in appearance or formation observed.

(19) It was possible to drill a hole in the object, polish it, coat it and paint it.

Example 5

(20) The powder mixture of Example 4 above was laid on the powder bed in Electro Optical Systems powder printer and with printer-head sprayed water between the layers. As a result, an object comprising layers was formed. The object was dried at room temperature for 24 hours. It was concluded that the powder mixture could be used in three-dimensional printing.

Example 6

(21) Water (104 g), oxalic acid (29 g), were mixed by Rodelys RS 300 stirrer at 250 rpm. Wood fibres (150), sander dust from spruce panels (92.0 g) were added slowly (over 30 min) and simultaneously into the mix under stirring of 180 rpm to provide a first homogenous paste composition.

(22) Water (101.7 g) was added to Prefere ExpL-3089 (174 g) under stirring of 300 rpm. Caprolactam (2 g) and Arbocel (89.5 g) were stirred in the mix, at 130 rpm. Corn starch (37 g) was added to provide a second homogenous paste composition.

Example 7

(23) Water (104 g), oxalic acid (29 g), were mixed by Rodelys RS 300 stirrer at 250 rpm. Wood fibres (150), sander dust from amino resin bonded spruce MDF boards (97.7 g) were added slowly (over 30 min) and simultaneously into the mix under stirring of 180 rpm to provide the first homogenous paste composition.

(24) Water (100 g) was added to Prefere ExpL-3089 (170 g) under stirring of 300 rpm. Caprolactam (2 g) and Arbocel (89.5 g) were stirred in the mix, at 130 rpm. Corn starch (37 g) was added to provide a second homogenous paste composition.

Example 8

(25) Water (109 g), oxalic acid (30.5 g), were mixed by Rodelys RS 300 stirrer at 250 rpm. Wood fibres (150 g), sawing dust from amino resin bonded pine particle board (87.2 g) were added slowly (over 30 min) and simultaneously into the mix under stirring of 180 rpm to provide a first homogenous paste composition.

(26) Water (100 g) was added to Prefere ExpL-3089 (174 g) under stirring of 300 rpm. Caprolactam (2 g) and Arbocel (89.5 g) were stirred in the mix, at 130 rpm. Corn starch (37 g) was added to provide a second homogenous paste composition.

Example 9

(27) Water (106 g), oxalic acid (31.5 g), were mixed by Rodelys RS 300 stirrer at 250 rpm. Wood fibres (150), bamboo fibres (85 g) were added slowly (over 30 min) and simultaneously into the mix under stirring of 180 rpm to provide a first homogenous paste composition.

(28) Water (100 g) was added to Prefere ExpL-3089 (179.2 g) under stirring of 300 rpm. Caprolactam (2 g) and Arbocel (89.5 g) were stirred in the mix, at 130 rpm. Corn starch (37 g) was added to provide second homogenous paste composition.

Example 10

(29) The mixture from example 7 where the first composition was prepared by mixing Water (104 g) and oxalic acid (29 g) by Rodelys RS 300 stirrer at 250 rpm, and later added wood fibres (150), sander dust from amino resin bonded spruce MDF boards (97.7 g) over 30 min into the existing mix under stirring of 180 rpm to provide the homogenous paste composition.

(30) The second composition was prepared by mixing Prefere ExpL-3089 (170 g) into water (100 g) under stirring of 300 rpm. Caprolactam (2 g) and Arbocel (89.5 g) were stirred in the mix, at 130 rpm. Corn starch (37 g) was added to provide second homogenous paste composition.

(31) The first and the second composition were transferred into separate plastic patrons and were joined with Y-joint. Y-joint was connected to the Archimedes screw. Pressure was applied on the top of the patrons, and the two compositions were mixed in site prior to extrusion through nozzle of size of 7×5 mm. In this document, mm refers to millimetres. The layers that we extruded were in the size of ca 7×5 mm. The mixture was flowing at the point of extrusion, but as soon as it was laid on the extrusion surface, the mixture was stiff and if became hard on touch within a few seconds.

Example 11

(32) In yet another example water (90 g), formic acid (19 g), were mixed by Rodelys RS 300 stirrer at 250 rpm. Wood fibres (150), sander dust from spruce panels (92.0 g) were added slowly (over 30 min) and simultaneously into the mix under stirring of 180 rpm to provide the first homogenous paste composition.

(33) Water (101.7 g) was added Prefere ExpL-3089 (174 g) under stirring of 300 rpm. Caprolactam (2 g) and Arbocel (89.5 g) were stirred in the mix, at 130 rpm. Corn starch (37 g) was added to provide second homogenous paste composition.

(34) The first and the second composition was transferred into separate plastic patrons, and we joined with Y-joint. Y-joint was connected to the Archimedes screw. Pressure was applied on the top of the patrons, and the two compositions were mixed in site prior to extrusion through nozzle with a diameter of 0.4 mm.

(35) Layer of size achieve of 0.5 mm (width)×0.5 mm (height) was extruded, and it was cured by the extrusion of the next layer.