CN114933483A

CN114933483A - 3D printing material, 3D printing product, refractory and preparation method thereof

Info

Publication number: CN114933483A
Application number: CN202210746888.8A
Authority: CN
Inventors: 刘黎; 易卫东; 孔勇江; 秦世民; 韩元庭
Original assignee: Wuhan Iron and Steel Co Ltd
Current assignee: Wuhan Iron and Steel Co Ltd
Priority date: 2022-06-28
Filing date: 2022-06-28
Publication date: 2022-08-23

Abstract

The application provides a 3D printing material, 3D printing material includes the raw materials of following parts by mass: 50-70 parts of refractory material, 20-40 parts of 3D printing polymer, 1-3 parts of silicon powder, 5-10 parts of plasticizer, 3-8 parts of volume stabilizer, 0.1-0.2 part of dispersant and 0.05-0.1 part of curing agent. The application provides a 3D prints material through printing polymer, silica flour, plasticizer, volume stabilizer, dispersant, curing agent to refractory material, 3D and compounding for volume change is little among the 3D prints material cooling forming process, and the mould precision of formation is easily controlled, and can not take place the volume shrinkage when carbonizing under the high temperature, can keep the refractory product's in the mould shape unchangeable.

Description

3D printing material, 3D printing product, refractory and preparation method thereof

Technical Field

The application relates to the field of fire resistance, in particular to a 3D printing material, a 3D printing product, a fire-resistant object and a preparation method thereof.

Background

The manufacture of refractory products of complex construction is a difficult point in the industry. The refractory material belongs to a brittle material, and the reprocessing difficulty of the shaped refractory product is high, so when a complex structure is involved, taking a special-shaped refractory product as an example, the current manufacturing process is that the shape of the special-shaped refractory product is divided into a plurality of blocks according to geometric characteristics, the blocks are respectively manufactured, the prepared refractory raw materials are poured and shaped, and the blocks are assembled and built on a construction site after maintenance, demolding and baking, so that the process is long, time and labor are wasted, and the production cost is high.

The 3D printing material can be used for integrally manufacturing a mold with a complex structure, but the volume of the 3D printing material is easy to change in the cooling and forming process, so that the precision of the formed mold is difficult to control. Meanwhile, when the polymer-based 3D printing material product is used as a mold for a fire-resistant product, it may be carbonized at a high temperature and undergo volume shrinkage to cause a change in shape of milk or a product.

Disclosure of Invention

The embodiment of the application provides a 3D printing material, a 3D printing product, a refractory and a preparation method thereof, and aims to solve the technical problem that the precision of a mold formed by 3D printing is difficult to control.

In a first aspect, an embodiment of the present application provides a 3D printing material, where the 3D printing material includes the following raw materials in parts by mass: 50-70 parts of refractory material, 20-40 parts of 3D printing polymer, 1-3 parts of silicon powder, 5-10 parts of plasticizer, 3-8 parts of volume stabilizer, 0.1-0.2 part of dispersant and 0.05-0.1 part of curing agent.

In some embodiments of the present application, the 3D printing material is composed of the following raw materials in parts by mass: 50-70 parts of refractory material, 20-40 parts of 3D printing polymer, 1-3 parts of silicon powder, 5-10 parts of plasticizer, 3-8 parts of volume stabilizer, 0.1-0.2 part of dispersant and 0.05-0.1 part of curing agent.

In some embodiments of the present application, the refractory material has a particle size of 0.04-0.05mm, and/or the 3D printed polymer has a particle size of 0.04-0.05 mm.

In some embodiments of the present application, the refractory material is selected from at least one of a corundum refractory material, a mullite refractory material, an alumina refractory material, an aluminum magnesium spinel refractory material, a zirconium corundum refractory material.

In some embodiments of the present application, the 3D printing polymer is at least one of polylactic acid, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-acrylic-styrene copolymer, polyamide, polycarbonate, polybutylene terephthalate, polyethylene terephthalate, polypropylene, polyvinyl butyral, high impact polystyrene, polycaprolactone, polystyrene, polyphenylsulfone, polyetheretherketone.

In some embodiments of the present application, the silicon powder is micron-sized silica having a surface modified with a silane coupling agent.

In some embodiments of the present application, the plasticizer is at least one of plastic clay, bentonite, soy flour, dextrin, and/or,

the volume stabilizer is at least one of kyanite powder, andalusite powder and sillimanite powder, and/or,

the dispersant is at least one of sodium lignosulphonate, sodium tripolyphosphate and sodium hexametaphosphate, and/or,

the curing agent is urotropin.

In a second aspect, embodiments of the present application provide a 3D printed article obtained by 3D printing the aforementioned 3D printed material.

In a third aspect, embodiments herein provide a refractory comprising a shaped refractory material and the 3D printed article of claim 8, the 3D printed article having an internal cavity, the shaped refractory material being filled in the internal cavity.

In a fourth aspect, embodiments of the present application provide a method for preparing a refractory, including the following steps:

providing the 3D printing material, and manufacturing a 3D printing product with an inner cavity through 3D printing;

providing raw materials of a shaped refractory material, and filling the raw materials of the shaped refractory material into the inner cavity;

and curing and baking the raw materials of the shaped refractory material to form the shaped refractory material.

Compared with the prior art, the technical scheme provided by the embodiment of the application has the following advantages:

the 3D printing material that this application embodiment provided is through printing polymer, silica flour, plasticizer, volume stabilizer, dispersant, curing agent to refractory material, 3D and compounding for volume change is little in the 3D printing material cooling forming process, and the mould precision of formation is easily controlled, and can not take place the volume shrink when carbonizing under the high temperature, can keep the shape of the refractory product in the mould unchangeable.

Drawings

The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and, together with the description, serve to explain the principles of the application.

In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.

Fig. 1 is a schematic flow chart of a method for preparing a 3D printing material provided in an embodiment of the present application;

fig. 2 is a schematic flow chart of a method for preparing a refractory according to an embodiment of the present disclosure.

Detailed Description

The present application will be specifically explained below with reference to specific embodiments and examples, and the advantages and various effects of the present application will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are provided to illustrate and not to limit the application.

Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. If there is a conflict, the present specification will control.

Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present application are commercially available or can be prepared by an existing method.

The existing 3D printing material has the technical problems that the volume change is large during cooling and forming, and the precision of a formed die is difficult to control.

In order to solve the technical problems, the general idea of the technical scheme provided by the embodiment of the application is as follows:

As will be understood by those skilled in the art, the refractory material refers to an inorganic non-metallic material having a refractoriness of not less than 1580 ℃. The volume change rate of the refractory material along with the temperature is extremely low, the volume change of the 3D printing material in the cooling forming process can be reduced by adding the refractory material, and the high-temperature resistance of the 3D printing material can be improved.

As can be understood by those skilled in the art, the 3D printing polymer is a polymer consumable in the field of 3D printing. The 3D printing polymer mainly provides processability for the 3D printing material, so that the 3D printing material can be melted and extruded by the 3D printing extrusion head for 3D printing.

As will be appreciated by those skilled in the art, the silicon powder functions to increase the bulk density of the 3D printed material, increase strength, decrease the coefficient of thermal expansion, and maintain volume stability.

As will be appreciated by those skilled in the art, the plasticizer functions to increase the flexibility of the 3D printed material.

As will be appreciated by those skilled in the art, the volume stabilizer reacts at high temperatures to cause expansion, which counteracts the shrinkage of the material at high temperatures, and results in volume stabilization of the material.

As will be appreciated by those skilled in the art, the dispersant functions to reduce the surface energy, avoid agglomeration between the materials, and improve dispersion.

As will be appreciated by those skilled in the art, the curing agent functions to rapidly cure the printed material to maintain the shape of the member.

As can be understood by those skilled in the art, the too high particle size of the refractory material or the 3D printing polymer has the adverse effect of being easy to block and damage the 3D printing nozzle, and the printing efficiency is affected, and the too low particle size of the refractory material or the 3D printing polymer has the adverse effect of being low in strength of the obtained finished product.

As will be understood by those skilled in the art, a corundum refractory refers to a refractory containing more than 390% Al2O and having a main crystal phase of α -Al2O 3.

As can be understood by those skilled in the art, the mullite refractory is a refractory which is prepared by taking artificial mullite as a raw material and takes mullite as a main crystal phase.

As will be appreciated by those skilled in the art, aluminous refractories are shaped refractory articles and unshaped refractories made from bauxite chamotte as the primary raw material.

As will be understood by those skilled in the art, the aluminum magnesium spinel refractory is a spinel refractory synthesized by high-temperature calcination of magnesium oxide and aluminum oxide as raw materials.

As will be appreciated by those skilled in the art, the zirconia-corundum refractory is a refractory formulated from zirconia-corundum particles and a small amount of additives

In some embodiments of the present application, the silicon powder is micron-sized silica having a surface modified with a silane coupling agent. The micron-sized silicon dioxide is modified by using the silane coupling agent, so that the dispersibility of the silicon powder in 3D printing macromolecules can be improved.

the curing agent is urotropin.

Referring to fig. 1, in some embodiments of the present application, a method for preparing the 3D printing material includes the following steps:

s11: providing the raw materials of each component of the 3D printing material;

s12: adding the raw materials into a ball mill, ball-milling, and sieving to obtain the 3D printing material.

In a third aspect, embodiments of the present application provide a refractory, where the refractory includes a shaped refractory material and the 3D printed product described above, where the 3D printed product has an inner cavity, and the shaped refractory material is filled in the inner cavity.

The shaped refractory material described herein is a shaped refractory product.

In some embodiments of the present application, the 3D printed article has a thickness of 3-7 mm. The 3D printing product is thin in thickness, can be used as a die for shaping refractory materials, and does not influence the refractory performance of the shaping refractory materials.

In a fourth aspect, please refer to fig. 2, an embodiment of the present application provides a method for preparing a refractory, comprising the following steps:

s21: providing the 3D printing material, and manufacturing a 3D printing product with an inner cavity through 3D printing;

s22: providing raw materials of a shaped refractory material, and filling the raw materials of the shaped refractory material into the inner cavity;

s23: and curing and baking the raw materials of the shaped refractory material to form the shaped refractory material.

The shaped refractory material described herein is a shaped refractory product.

The preparation method of the refractory provided by the embodiment of the application can be used for preparing the refractory in the third aspect.

According to the preparation method of the refractory material, the outer contour of the refractory material can be prepared through 3D printing, and the volume change of the outer contour in the cooling forming process is small, so that the precision is easy to control, and the refractory material can be used as a mold for shaping the refractory material.

The present application is further illustrated with reference to specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present application. The experimental methods of the following examples, which are not specified under specific conditions, are generally determined according to national standards. If there is no corresponding national standard, it is carried out according to the usual international standards, to the conventional conditions or to the conditions recommended by the manufacturer.

Example 1

Firstly, the present embodiment provides a 3D printing material, where the 3D printing material includes the following components by mass percent:

70% of refractory material with the granularity of 0.045 mm;

20% of 3D printing polymer with the granularity of 0.045 mm;

3% of silicon powder;

4% of a plasticizer;

3% of volume stabilizer;

0.1 percent of dispersant;

0.05 percent of curing agent.

Wherein, refractory material is corundum powder, and the 3D prints the polymer and is polylactic acid and polyether ether ketone with 1: 2, the plasticizer is a mixture of plastic clay and soybean flour in a mass ratio of 2: 1, and the volume stabilizer is a mixture of sapphire powder and andalusite powder in a mass ratio of 2: 1, and the dispersant is a mixture of sodium tripolyphosphate and sodium hexametaphosphate in a mass ratio of 1: 1, and the curing agent is urotropine.

The embodiment also provides a preparation method of the 3D printing material, which includes the following steps:

s1 a: adding the raw materials of the components into a ball mill, taking ceramic balls with the diameter of 8mm as grinding media, wherein the ball-material ratio is 1:7 by mass;

s1 b: ball milling for 100min at the stirring speed of 300r/min to obtain powder;

s1 c: and sieving the powder through a 325-mesh screen to obtain the 3D printing material.

This example also provides a refractory prepared by:

s2 a: printing the outer contour of the refractory by using the 3D printing material as a raw material, wherein the thickness of the outer contour is 5 mm;

s2 b: providing raw materials of the corundum refractory material, and filling the raw materials of the corundum refractory material into the outer contour by using a spray gun when the height of the outer contour is increased by 25 mm;

s3 b: and after the outer contour printing is finished and the raw materials of the corundum refractory material are completely filled, maintaining and baking the filled raw materials of the corundum refractory material to obtain the refractory.

Example 2

This example differs from example 1 in that:

the mass percentage of the refractory material is 60 percent;

the mass percentage of the 3D printing polymer is 28%;

the mass percent of the silicon powder is 1 percent;

the mass percent of the plasticizer is 6 percent;

the mass percentage of the volume stabilizer is 5 percent;

the mass percent of the curing agent is 0.07 percent.

The refractory material is mullite powder, the 3D printing polymer is acrylonitrile-butadiene-styrene copolymer, the plasticizer is plastic clay, and the volume stabilizer is sapphire powder and sillimanite powder, wherein the volume ratio of the sapphire powder to the sillimanite powder is 2: 1, and the dispersant is sodium hexametaphosphate mixed by the mass ratio of 1: 1 in a mass ratio.

Example 3

This example differs from example 1 in that:

the mass percent of the refractory material is 58 percent;

the mass percentage of the 3D printing polymer is 29%;

the mass percent of the silicon powder is 2 percent;

the mass percent of the plasticizer is 6 percent;

the mass percentage of the volume stabilizer is 5 percent;

the mass percent of the curing agent is 0.07 percent.

The refractory material is alumina powder, the 3D printing polymer is polypropylene, and the plasticizer is plastic clay and dextrin, wherein the mass ratio of the plastic clay to the dextrin is 3: 1, the volume stabilizer is kyanite powder, and the dispersant is sodium lignosulfonate.

Example 4

This example differs from example 1 in that:

the mass percent of the refractory material is 55 percent;

the mass percentage of the 3D printing polymer is 25%;

the mass percent of the silicon powder is 2%;

the mass percent of the plasticizer is 10 percent;

the mass percentage of the volume stabilizer is 8 percent;

the mass percent of the dispersant is 0.2 percent;

the mass percent of the curing agent is 0.1 percent.

The refractory material is aluminum magnesium spinel powder, the 3D printing polymer is polyethylene glycol terephthalate, and the plasticizer is bentonite and dextrin with the ratio of 4: 1, the volume stabilizer is silica powder, and the dispersant is sodium lignosulfonate.

Example 5

This example differs from example 1 in that:

the mass percentage of the refractory material is 60 percent;

the mass percentage of the 3D printing polymer is 27%;

the mass percent of the silicon powder is 2 percent;

the mass percent of the plasticizer is 6 percent;

the mass percentage of the volume stabilizer is 5 percent;

the mass percent of the dispersant is 0.1%;

the mass percent of the curing agent is 0.07 percent.

The refractory material is aluminum magnesium zirconium corundum powder, the 3D printing polymer is high impact polystyrene, the plasticizer is plastic clay, the volume stabilizer is kyanite powder, and the dispersing agent is sodium lignosulfonate.

It is noted that, in this document, relational terms such as "first" and "second," and the like, are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising … …" does not exclude the presence of additional identical elements in the process, method, article, or apparatus that comprises the element.

The above description is merely exemplary of the present application and is presented to enable those skilled in the art to understand and practice the present application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. The 3D printing material is characterized by comprising the following raw materials in parts by mass: 50-70 parts of refractory material, 20-40 parts of 3D printing polymer, 1-3 parts of silicon powder, 5-10 parts of plasticizer, 3-8 parts of volume stabilizer, 0.1-0.2 part of dispersant and 0.05-0.1 part of curing agent.

2. The 3D printing material according to claim 1, wherein the 3D printing material is composed of the following raw materials in parts by mass: 50-70 parts of refractory material, 20-40 parts of 3D printing polymer, 1-3 parts of silicon powder, 5-10 parts of plasticizer, 3-8 parts of volume stabilizer, 0.1-0.2 part of dispersant and 0.05-0.1 part of curing agent.

3. The 3D printed material according to claim 1, wherein the particle size of the refractory material is 0.04-0.05mm and/or the particle size of the 3D printed polymer is 0.04-0.05 mm.

4. The 3D printed material according to claim 1, wherein the refractory material is selected from at least one of a corundum refractory material, a mullite refractory material, an alumina refractory material, an aluminum magnesium spinel refractory material, a zirconium corundum refractory material.

5. The 3D printed material according to claim 1, wherein the 3D printing polymer is at least one of polylactic acid, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-acrylic acid-styrene copolymer, polyamide, polycarbonate, polybutylene terephthalate, polyethylene terephthalate, polypropylene, polyvinyl butyral, high impact polystyrene, polycaprolactone, polystyrene, polyphenylsulfone, polyetheretherketone.

6. The 3D printing material according to claim 1, wherein the silicon powder is micron-sized silica with a surface modified by a silane coupling agent.

7. 3D printed material according to claim 1,

the plasticizer is at least one of plastic clay, bentonite, soybean meal and dextrin, and/or,

the curing agent is urotropin.

8. A 3D printed article obtained by 3D printing of the 3D printed material according to any one of claims 1 to 7.

9. A refractory, characterized in that the refractory comprises a shaped refractory material and the 3D printed article of claim 8, the 3D printed article having an interior cavity, the shaped refractory material being filled in the interior cavity.

10. A method for preparing a refractory, comprising the steps of:

providing the 3D printed material of claim 1, made into a 3D printed article having an internal cavity by 3D printing;