CN111377699A - Gypsum powder for 3D printing - Google Patents
Gypsum powder for 3D printing Download PDFInfo
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- CN111377699A CN111377699A CN202010206135.9A CN202010206135A CN111377699A CN 111377699 A CN111377699 A CN 111377699A CN 202010206135 A CN202010206135 A CN 202010206135A CN 111377699 A CN111377699 A CN 111377699A
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- powder
- gypsum powder
- gypsum
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- printing
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
- C04B28/145—Calcium sulfate hemi-hydrate with a specific crystal form
- C04B28/146—Calcium sulfate hemi-hydrate with a specific crystal form alpha-hemihydrate
-
- 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
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00034—Physico-chemical characteristics of the mixtures
- C04B2111/00181—Mixtures specially adapted for three-dimensional printing (3DP), stereo-lithography or prototyping
Abstract
The invention relates to gypsum powder for 3D printing, which comprises, by mass, α -8990% of base material-hemihydrate gypsum, 10-25% of binder, 0.5-5% of coagulant, 0.5-2% of dispersant and 5-10% of other additives, wherein the particle size of the base material α -hemihydrate gypsum powder is 100-500 meshes.
Description
Technical Field
The invention relates to the field of 3D printing, in particular to gypsum powder for 3D printing.
Background
3D printing (3DP), one of the rapid prototyping technologies, is a technology that constructs an object by using a bondable material such as powdered metal, plastic, ceramic, sand, silicon carbide powder, gypsum material, etc., and printing layer by layer on the basis of a digital model file. 3D printing creates a solid body because the added material can be printed directly layer by a printer based on the three-dimensional data of the model. 3D printing is typically achieved using digital technology material printers. The technology has attracted high attention in manufacturing and other related fields and is known as the core technology of the third industrial technology revolution. Is used for manufacturing models or direct manufacturing of some products in the fields of mold manufacturing, industrial design and the like; the technology does not need the formwork supporting process of the traditional building material construction molding, thereby simplifying the construction process and shortening the construction working hours.
The material is not only the basis of the 3D printing technology, but also the bottleneck restricting the development of the 3D printing technology. Due to the characteristics of 3D printing, the used materials can be used for 3D printing only when specific performance requirements such as working, mechanics, safety performance, manufacturing cost and the like are met. The variety of materials applied to the 3D printing technology is wide, and the diversified development of the materials also becomes the main advantages of the materials. Most of materials applied to the 3D printing technology at present are engineering plastics, photosensitive resin, rubbers, metals, ceramics, gypsum and the like, wherein the gypsum has a wide development prospect as a material which is wide in material availability, low in price, easy to obtain, safe and harmless.
The gypsum material is an environment-friendly inorganic cementing material, has quick and controllable setting time, and can be completely used as a raw material for additive manufacturing technologies such as 3D printing and the like. The gypsum powder is used as a rapid forming material, and has the advantages of high forming speed, good forming precision and strength, low price, no toxicity, no pollution and the like, and a proper post-processing mode is adopted, so that the formed part has high strength and is not easy to deform, the gypsum powder can replace the existing plastic and resin models in some occasions, and the gypsum powder can be used as a concept prototype, a prototype of a function test, a mold and a functional part, and is more favorable for popularization of a rapid forming technology. However, the conventional plaster has the following defects if directly used for 3D printing: 1. the strength of the printed product is low; 2. slow curing, which affects printing efficiency; 3. the printed product boundary spreads to influence the printing precision of the product; 4. high water absorption and poor water resistance; 5. poor fluidity and unsmooth blanking in the printing process. The above disadvantages greatly limit the application of gypsum materials in the field of additive manufacturing, and also hinder the appearance and development of new gypsum products with optimally designed structures and excellent properties, which the prior art has not addressed.
Therefore, how to design a gypsum powder specially used for 3D printing becomes a problem to be solved urgently in the field, and has important practical significance and practical value.
Disclosure of Invention
Aiming at the defects of low strength, slow curing, diffusion of printed product boundary, high water absorption, poor water resistance and the like of the printed product in the prior art, the invention provides gypsum powder for 3D printing, and effectively solves the defects in the prior art. The gypsum powder has the advantages of high forming and hardening speed, proper permeation, high forming precision, high strength, no toxicity, environmental protection, simple production process, low cost and the like.
In order to solve the defects, the invention adopts the technical scheme that:
the gypsum powder for 3D printing comprises, by mass, α -90% of base material-hemihydrate gypsum, 10-25% of binder, 0.5-5% of coagulant, 0.5-2% of dispersant and 5-10% of other auxiliaries.
Furthermore, the granularity of the base material α -hemihydrate gypsum powder is 100-500 meshes.
Furthermore, the particle size of the base material α -hemihydrate gypsum powder is 125-325 meshes, and the addition amount of the base material α -hemihydrate gypsum powder is 75-85%.
Further, the binder is one or more of methylcellulose, hydroxypropyl methylcellulose, sodium carboxymethylcellulose, hydroxyethyl cellulose, polyvinyl alcohol, redispersible latex powder, maltodextrin and starch.
Further, the adhesive is 5% -20% of polyvinyl alcohol with 200-325 meshes and 1-5% of hydroxyethyl cellulose, and the ratio of the polyvinyl alcohol to the hydroxyethyl cellulose is 1: 1-10: 1.
Further, the coagulant is one or more of sodium sulfate, potassium sulfate, magnesium sulfate, dihydrate gypsum, potassium nitrate, sodium sulfate, sodium bicarbonate, sodium oxalate, calcium dimetaphosphate and alum.
Further, the coagulant is 2000-mesh dihydrate gypsum, potassium sulfate or sodium sulfate, and the addition amount of the coagulant is 0.5-5%.
Further, the dispersing agent is white carbon black with the particle size of 7-40 nm, and the specific surface area is more than 100m2The content of silicon dioxide is more than or equal to 99.8 percent.
Further, the other auxiliary agents comprise one or more of 200-325 meshes of silicon dioxide, alumina powder, soluble starch, talcum powder and lecithin.
Furthermore, the adding amount of the silicon dioxide, the alumina powder, the soluble starch and the talcum powder is 2-5%, and the adding amount of the lecithin is 0.5-2%.
Compared with the prior art, the method of the invention has the following beneficial effects:
the gypsum powder for 3D printing has the advantages of high forming and hardening speed, proper permeation, high forming precision, good strength, no toxicity and environmental protection; the gypsum powder is uniform, fine and smooth, and has no agglomeration; the powder has good fluidity, so that a powder supply system is not easy to block, the powder can be paved into a thin layer, the powder paving is uniform and smooth, no wrinkles exist, no powder flies, the printing head cannot be blocked, the effect is ideal, the raw materials are cheap and suitable, the production process is simple, and the production cost is effectively reduced.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the accompanying examples. The preferred embodiments of the present invention are given in the examples. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
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 invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In order to solve the defects, the invention adopts the technical scheme that:
the gypsum powder for 3D printing comprises, by mass, α -90% of base material-hemihydrate gypsum, 10-25% of binder, 0.5-5% of coagulant, 0.5-2% of dispersant and 5-10% of other auxiliaries.
The α -hemihydrate gypsum powder is smaller than β -hemihydrate gypsum in water-paste ratio, the smaller the water-paste ratio is, the faster the gypsum setting speed is, the higher the strength of a product is, the smaller the water absorption rate is, the granularity of gypsum powder has a larger influence on product performance, the granularity of the powder directly influences the precision of layer-by-layer forming, and influences the wetting and capillary penetration of liquid drops, the larger powder particles have smaller surfaces and are not easy to penetrate and bond with other particles in the wetting process of the liquid drops, on the contrary, the finer powder particles are easy to bond and form, but if the granularity is too fine, flocculation particles are easy to form, namely, the powder is easy to agglomerate, so that the powder is not easy to be paved into a thin layer, and the powder is easy to bond to the surface of a roller, and the forming precision is influenced, and the base α -hemihydrate gypsum powder has the granularity of 100-500 meshes.
Further, the gypsum content has a great influence on the performance of the printed product, the greater the gypsum content is, the greater the product density and compressive strength are, but the greater the dimensional deformation of the product is, the lower the gypsum content is, the poorer the strength and surface quality of the product is, when the content of the base material α -hemihydrate gypsum powder is between 70% and 90%, the better the surface quality is, and the addition amount of the base material α -hemihydrate gypsum powder is preferably 75-85%.
Further, the binder is one or more of methylcellulose, hydroxypropyl methylcellulose, sodium carboxymethylcellulose, hydroxyethyl cellulose (HEC), polyvinyl alcohol (PVA), re-dispersible latex powder, maltodextrin and starch.
The binder is used as a raw material for enhancing the powder binding power, and can play a role in enhancing the powder forming strength; the good cohesiveness and film forming property of polyvinyl alcohol are utilized, the resolution and the forming precision of a three-dimensional printing forming part can be obviously improved, and the polyvinyl alcohol (PVA) is added to make up for the defects of the hardness and the compressive strength of gypsum. As the long molecular chain can cause the powder adhesion phenomenon in the printing process, the 200-325-mesh polyvinyl alcohol with short molecular chain, low viscosity and good bonding strength is selected as the bonding agent. Proper amount PVA has very big improvement to the compressive strength of powder, but too much PVA not only can make the viscosity greatly increased after mixing with water, influences the roll nature of powder, reduces powder density, leads to the material shaping not good, and PVA's water retention ability is stronger moreover, is unfavorable for quick shaping and the drying of part after the shaping to consider the influence to density porosity, PVA chooses the addition at 5 ~ 20%. The addition of a small amount of hydroxyethyl cellulose (HEC) can simultaneously function as a binder, water retention agent and reinforcing agent. The PVA and the HEC are used simultaneously and can play a role in mutual cooperation, and the adding ratio of the PVA to the HEC is 1: 1-5: 1; PVA and HEC can affect the hydration of the hemihydrate gypsum and thus the macroscopic properties of the article. The binder comprises 5-20% of 200-325-mesh polyvinyl alcohol and 1-5% of hydroxyethyl cellulose, and the ratio of the polyvinyl alcohol to the hydroxyethyl cellulose is 1: 1-10: 1.
Further, the coagulant is one or more of sodium sulfate, potassium sulfate, magnesium sulfate, dihydrate gypsum, potassium nitrate, sodium sulfate, sodium bicarbonate, sodium oxalate, calcium dimetaphosphate and alum; the coagulant is preferably 2000-mesh dihydrate gypsum, potassium sulfate or sodium sulfate, the addition amount of the coagulant is 0.5-5%, and the coagulant is most preferably dihydrate gypsum.
Further, the dispersing agent is white carbon black, the primary particle size of the white carbon black is 7-40 nm, the specific surface area is more than 100m2/g, and the content of silicon dioxide is more than or equal to 99.8%. As the content of the white carbon black is too high, the cohesive property, the product strength and the like of the powder can be influenced, and the adding amount of the white carbon black is not too high, the preferable adding amount of the white carbon black is 0.5-2%.
Further, the other auxiliary agents comprise one or more of 200-325 meshes of silicon dioxide, alumina powder, soluble starch, talcum powder and lecithin. The addition amount of the silicon dioxide, the alumina powder, the soluble starch and the talcum powder is 2-5%, and the addition amount of the lecithin is 0.5-2%.
A preparation method of gypsum powder for 3D printing specifically comprises the following steps:
① adding α -hemihydrate gypsum, binder, coagulant, dispersant and other adjuvants into a tank mixer in sequence according to the proportion of the binder, the coagulant, the dispersant and other adjuvants
The zirconia solid spheres are ball milling media, ball milling is carried out for 0.5-2 h under the conditions that the ball milling media are added in a mass ratio of 3: 1-5: 1 and the stirring speed is 200-1000 r/min, so that various powder materials are fully and uniformly mixed to prepare gypsum powder;
② placing the gypsum powder in a vacuum drying oven for heat drying treatment at 80-100 deg.C for 2-5 h, and filtering with 200 mesh screen to obtain the final product.
Specific examples, as shown in table 1, the embodiments are as described above.
Table 1 specific examples of gypsum powder for 3D printing
Note: the data are mass percent
Example one:
① adding 30% of α -hemihydrate gypsum of 200-270 meshes, 45% of α -hemihydrate gypsum of 270-325 meshes, 10% of polyvinyl alcohol, 5% of hydroxyethyl cellulose, 1.5% of anhydrite, 0.5% of white carbon black, 0.5% of silicon dioxide, 4% of alumina powder and 1% of lecithin into a pot mixer in sequence, and mixing the materials to obtain the product with the diameter of 1%
The zirconia solid sphere is a ball milling medium, and the ball milling medium is added in a mass ratio of 3: 1E5:1 and ball milling for 0.5-2 h under the condition that the stirring speed is 200-1000 r/min, so that various powder materials are fully and uniformly mixed to prepare gypsum powder materials;
② placing the gypsum powder in a vacuum drying oven for thermal drying at 100 deg.C for 2 hr, and filtering with 200 mesh screen to obtain the final product.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The gypsum powder for 3D printing is characterized by comprising, by mass, α -90% of base material-hemihydrate gypsum, 10-25% of binder, 0.5-5% of coagulant, 0.5-2% of dispersant and 5-10% of other auxiliaries.
2. The gypsum powder for 3D printing according to claim 1, wherein the base material α -hemihydrate gypsum powder has a particle size of 100-500 mesh.
3. The gypsum powder for 3D printing according to claims 1-2, wherein the base material α -hemihydrate gypsum powder has a particle size of 125-325 mesh, and the base material α -hemihydrate gypsum powder is added in an amount of 75-85%.
4. The gypsum powder for 3D printing according to claim 1, wherein the binder is one or more of methylcellulose, hydroxypropyl methylcellulose, sodium carboxymethylcellulose, hydroxyethyl cellulose, polyvinyl alcohol, redispersible latex powder, maltodextrin, and starch.
5. The gypsum powder for 3D printing according to claim 4, wherein the binder comprises 5-20% of 200-325 mesh polyvinyl alcohol and 1-5% of hydroxyethyl cellulose, and the ratio of the polyvinyl alcohol to the hydroxyethyl cellulose is 1: 1-10: 1.
6. The gypsum powder for 3D printing according to claim 1, wherein the set accelerator is one or more of sodium sulfate, potassium sulfate, magnesium sulfate, dihydrate gypsum, potassium nitrate, sodium sulfate, sodium bicarbonate, sodium oxalate, calcium dimetaphosphate, and alum.
7. The gypsum powder for 3D printing according to claim 6, wherein the coagulant is 2000-mesh dihydrate gypsum, potassium sulfate or sodium sulfate, and the addition amount of the coagulant is 0.5-5%.
8. The gypsum powder for 3D printing according to claim 1, wherein the dispersing agent is white carbon black with a particle size of 7-40 nm, the specific surface area is more than 100m2/g, and the content of silicon dioxide is more than or equal to 99.8%.
9. The gypsum powder for 3D printing according to claim 1, wherein the other additives comprise one or more of 200-325 mesh silica, alumina powder, soluble starch, talc and lecithin.
10. The gypsum powder for 3D printing according to claim 9, wherein the silica, alumina powder, soluble starch and talc are added in an amount of 2-5%, and the lecithin is added in an amount of 0.5-2%.
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| CN202010206135.9A CN111377699A (en) | 2020-03-24 | 2020-03-24 | Gypsum powder for 3D printing |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112759298A (en) * | 2021-01-04 | 2021-05-07 | 河北工业大学 | Material for powder 3D printing test model and preparation method thereof |
| CN113185254A (en) * | 2021-06-18 | 2021-07-30 | 倪金花 | Quick-adhesion powder for gypsum line space filling |
| CN113637357A (en) * | 2021-08-26 | 2021-11-12 | 共享智能铸造产业创新中心有限公司 | Inorganic single-component ink for gypsum printing and preparation method thereof |
| CN113666703A (en) * | 2021-08-20 | 2021-11-19 | 河南永泰石膏有限公司 | 3D printing gypsum powder and preparation method thereof |
| CN115611601A (en) * | 2022-11-07 | 2023-01-17 | 同济大学 | Gypsum 3D printing powder and preparation method and application thereof |
| CN116041025A (en) * | 2023-01-11 | 2023-05-02 | 同济大学 | Method for circularly preparing 3D printing sound absorbing material by using waste gypsum board |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1850694A (en) * | 2006-05-15 | 2006-10-25 | 中北大学 | Gypsum base material system for 3-D spraying binding and preparing method therefor |
| CN1865330A (en) * | 2006-05-15 | 2006-11-22 | 中北大学 | Starch base material system for tridimensional spraying and adhesive bonding and preparation method thereof |
| CN104744000A (en) * | 2015-03-07 | 2015-07-01 | 南京工业大学 | Gypsum material for 3D printing and preparation method thereof |
| KR20160112495A (en) * | 2015-03-19 | 2016-09-28 | 한국과학기술연구원 | Ink Compositions for a Powder Bed and Inkjet Head-Based 3D Printer |
| CN106009441A (en) * | 2016-05-18 | 2016-10-12 | 重庆云图蓝谷科技有限公司 | Material for three-dimensional printing and preparation method of material |
-
2020
- 2020-03-24 CN CN202010206135.9A patent/CN111377699A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1850694A (en) * | 2006-05-15 | 2006-10-25 | 中北大学 | Gypsum base material system for 3-D spraying binding and preparing method therefor |
| CN1865330A (en) * | 2006-05-15 | 2006-11-22 | 中北大学 | Starch base material system for tridimensional spraying and adhesive bonding and preparation method thereof |
| CN104744000A (en) * | 2015-03-07 | 2015-07-01 | 南京工业大学 | Gypsum material for 3D printing and preparation method thereof |
| KR20160112495A (en) * | 2015-03-19 | 2016-09-28 | 한국과학기술연구원 | Ink Compositions for a Powder Bed and Inkjet Head-Based 3D Printer |
| CN106009441A (en) * | 2016-05-18 | 2016-10-12 | 重庆云图蓝谷科技有限公司 | Material for three-dimensional printing and preparation method of material |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112759298A (en) * | 2021-01-04 | 2021-05-07 | 河北工业大学 | Material for powder 3D printing test model and preparation method thereof |
| CN113185254A (en) * | 2021-06-18 | 2021-07-30 | 倪金花 | Quick-adhesion powder for gypsum line space filling |
| CN113666703A (en) * | 2021-08-20 | 2021-11-19 | 河南永泰石膏有限公司 | 3D printing gypsum powder and preparation method thereof |
| CN113637357A (en) * | 2021-08-26 | 2021-11-12 | 共享智能铸造产业创新中心有限公司 | Inorganic single-component ink for gypsum printing and preparation method thereof |
| CN115611601A (en) * | 2022-11-07 | 2023-01-17 | 同济大学 | Gypsum 3D printing powder and preparation method and application thereof |
| CN116041025A (en) * | 2023-01-11 | 2023-05-02 | 同济大学 | Method for circularly preparing 3D printing sound absorbing material by using waste gypsum board |
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Application publication date: 20200707 |