The preparation method of ceramic core printed material and preparation method thereof and ceramic core
Technical field
The present invention relates to three Dimensional Printing of Rapid Prototyping technical field, more particularly, to a kind of ceramic core printed material and
The preparation method of preparation method and ceramic core.
Background technique
Ceramic mold casting is a kind of new process to grow up on the basis of sand casting and model casting, is accurate casting
One of main method made is widely used in hot investment casting production.Currently, the production of ceramic core used in ceramic mold casting
Main method is after being made into slurry with refractory material, to pass through filling using mold using the hydrolyzate of silester as binder
The techniques such as slurry, gum deposit, molding, roasting are fired.The production method contains the design and production of mold, due to a kind of mold
The ceramic core that a kind of specific structure can only be produced also needs to make certain moduli tool when the ceramic core that production is becomed privileged,
The production of mold needs to expend a large amount of cost of labor and material cost, and therefore, the production method is for becoming privileged ceramic core
For, high production cost;In addition, the shape for the ceramic core being prepared using the production method also will be by Mold Making energy
The limitation of power;In addition, existing mold no longer has the value utilized substantially, also after ceramic core structure is changed
Produce a large amount of mold waste.
Three Dimensional Printing of Rapid Prototyping technology (Three Dimensional Printing and Gluing, abbreviation 3DP) with
Other rapid prototyping technologies are compared and are had many advantages, it is considered to be one of most vital new technology in Quick-forming field,
With vast potential for future development.
Although 3DP technology can be realized 3D printing, requirement of the technology for printed material is relatively high, existing market
On also lack a kind of ceramic core printed material that can be suitable for 3DP technology.
In view of this, the present invention is specifically proposed.
Summary of the invention
It is above-mentioned to alleviate one of the objects of the present invention is to provide a kind of ceramic core printed material and preparation method thereof
At least one of technical problem.
Another object of the present invention is to provide a kind of preparation method of ceramic core, which can alleviate above-mentioned
The problem of existing ceramic core preparation process.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
A kind of ceramic core printed material, including molding powder, according to parts by weight, the molding powder includes fire resisting
85~93.5 parts of aggregate, 4.5~10 parts of reinforcing agent, 1~2.5 part of curing agent and 1~2.5 part of dispersing agent.
Further, the 3D printing material includes liquid-containing binder, and according to parts by weight, the liquid-containing binder includes
68~90 parts of adhesion component, 9~30 parts of diluent and 1~2 part of surfactant;Wherein, the binder and the diluent
Total weight number be 98~99 parts.
A kind of preparation method of ceramic core printed material, comprising the following steps:
A) powder I will be obtained after the mixture pelleting of refractory aggregate and reinforcing agent;
B) powder II will be obtained after curing agent and dispersant;
C powder I and powder II) are mixed into sieving and obtain the molding powder.
A kind of preparation method of ceramic core printed material, comprising the following steps:
A) molding powder is prepared using preparation method described in claim 7 or 8;
B) liquid-containing binder is obtained after mixing binder, diluent with surfactant.
A kind of preparation method of ceramic core provides above-mentioned ceramic core and uses printed material as printing raw material, utilizes 3DP
Technology printing shaping, obtains ceramic core.
Compared with the prior art, the invention has the following beneficial effects:
Ceramic core printed material provided by the invention, using refractory aggregate as main component, by adding specific proportion
Reinforcing agent, curing agent and dispersing agent improve the mobility of molding powder, improve the fire resistance of printed product, compression strength and anti-
Curved intensity.Experiment proves that molding powder fluidity is good in printed material provided by the invention, the powdering used with printing technology
The adaptability of device is good, and minimum powdering thickness can achieve 0.08mm, can significantly improve printing precision using the molding powder.
Ceramic core can be directly printed using printed material provided by the invention, efficiently solves and is prepared currently with tradition
The problem of mold wastes when method prepares ceramic core.Using printed material provided by the invention can direct printing shaping, relatively
Reduce processing step in traditional preparation methods, improves production efficiency.
In addition, after using molding powder provided by the invention and liquid-containing binder printing shaping, obtained ceramic core base
The compression strength of body can achieve 3MPa or more, which can guarantee that ceramic core green body will not be damaged when clearing up powder,
Facilitate the cleaning of powder on printing equipment platform.
After powder for molding provided by the invention and liquid-containing binder printing shaping, ceramic core green body is through 800-1000
The high-temperature bending strength of ceramic core obtained after DEG C baking can reach 8MPa or more, and ceramic core is run in casting use process
Fiery rate is low, and the good permeability of ceramic core, and the surface quality of continuous castings cast is good, and dimensional accuracy is high.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
On the one hand, the present invention provides a kind of ceramic core printed materials, including molding powder, according to parts by weight,
The molding powder include 85~93.5 parts of refractory aggregate, 4.5~10 parts of reinforcing agent, 1~2.5 part of curing agent and dispersing agent 1~
2.5 part.
Ceramic core printed material provided by the invention, using refractory aggregate as main component, by adding specific proportion
Reinforcing agent, curing agent and dispersing agent improve the mobility of molding powder, improve the fire resistance of printed product, compression strength and anti-
Curved intensity.Experiment proves that molding powder fluidity is good in printed material provided by the invention, the powdering used with printing technology
The adaptability of device is good, and minimum powdering thickness can achieve 0.08mm, can significantly improve printing precision using the molding powder.
Theoretically, it is any can be fabricated to powdered material can be with 3DP technological forming, material selection range is very
Extensively.The maximum of this technology development at present hinders material needed for being that molding, and main includes molding powder and liquid-containing binder
Two parts, and the quality for forming powder characteristic is directly related to the quality of printed product.It is each that the present invention is exactly based on rationally setting
The proportion of constitutive material, to improve shaping strength, agglomeration, rollability, density and the porosity etc. of molding powder, to meet
The printing requirement of 3DP technique, to prepare the ceramic core of function admirable.
In ceramic core printed material in the present invention, according to parts by weight, the weight of refractory aggregate in powder is formed
Number for example can be 85 parts, 86 parts, 87 parts, 88 parts, 89 parts, 90 parts, 91 parts, 92 parts, 93 parts or 93.5 parts;The weight of reinforcing agent
Measuring number for example can be 4.5 parts, 5 parts, 5 parts, 7 parts, 8 parts, 9 parts or 10 parts;The parts by weight of curing agent for example can be 1
Part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts or 2.5 parts;The parts by weight of dispersing agent for example can be 1 part, 1.2
Part, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts or 2.5 parts.
In some preferred embodiments of the invention, according to parts by weight, the molding powder includes refractory aggregate 86
~93 parts, 5~8 parts of reinforcing agent, 1.5~2.5 parts of curing agent and 1.5~2.5 parts of dispersing agent;Of the invention further preferred
In embodiment, according to parts by weight, the molding powder includes 87~92 parts of refractory aggregate, 6~8 parts of reinforcing agent, curing agent
1.5~20 parts and 1.5~2.0 parts of dispersing agent.Preferably, the mass ratio of the curing agent and the dispersing agent is 1:1.By excellent
The composition of chemical conversion type powder material can be further improved the properties of molding powder, such as: shaping strength, agglomeration, rolling
Dynamic property, density and porosity etc..
In certain embodiments of the present invention, refractory aggregate for example can be mullite powder, schmigel, silica flour or zirconium
One of English powder or at least two combination.By limiting the raw material of refractory aggregate, the fire resisting of refractory aggregate both can be improved
Property can also improve the intensity of refractory aggregate.
In certain embodiments of the present invention, the particle size distribution of the refractory aggregate are as follows: 400 mesh percent of pass >=
98%.For opposite other conditions, the partial size for forming powder is extremely important.When the partial size of refractory aggregate is too small, between particle
Intermolecular force it is stronger, be easy to happen reunion, rollability is poor, be easy blocking spray head;When the partial size of refractory aggregate is larger
When, the rollability of particle is good, but easy to fall off in print procedure, and will affect printing precision.Therefore, suitable particle diameter distribution
It is the premise and basic guarantee for improving printed product quality.In embodiments of the present invention, pass through the grain of restriction refractory aggregate
Degree distribution can be further improved printing precision, to improve the presentation quality and intensity of printed product.
In certain embodiments of the present invention, the reinforcing agent is phosphate, salt of phosphoric acid or silicate, preferably phosphorus
Acid dihydride aluminium powder body or sodium metasilicate powder;Wherein, in preferred embodiment, the matter of the aluminium dihydrogen phosphate in the aluminium dihydrogen phosphate powder
Measure percentage composition >=98%;In further preferred embodiment, the particle size distribution of the aluminium dihydrogen phosphate powder are as follows: 200 mesh
Sieve percent of pass >=98%.
By selecting aluminium dihydrogen phosphate as reinforcing agent and by the content and powder granule grain of optimization aluminium dihydrogen phosphate
Diameter can significantly improve the resistance to pressure of the ceramic core obtained after the intensity and sintering of the ceramic core green body obtained after printing
Degree.
In certain embodiments of the present invention, the curing agent includes one of magnesia, copper oxide or zinc oxide
Or at least two combination;In preferred embodiment, the particle size distribution of the curing agent are as follows: 200 mesh percent of pass >=98%.
Curing agent can be reacted with binder generates the higher product of adhesive property, facilitates blank forming;For example, curing agent can be with
Biphosphate reactive aluminum in binder liquid generates the higher products of adhesive properties such as aluminum phosphate.
In certain embodiments of the present invention, the dispersing agent is fumed silica, stearic acid or stearate;?
In further preferred embodiment, specific surface area >=200m of the fumed silica2/g。
Printed material provided by the invention includes liquid-containing binder, and according to parts by weight, the liquid-containing binder includes viscous
68~90 parts of component of knot, 9~30 parts of diluent and 1~2 part of surfactant;Wherein, the binder and the diluent
Total weight number is 98~99 parts.
The liquid-containing binder that above embodiment of the present invention provides, viscosity is 8~20mPas under room temperature, and surface tension is
25~38mN/m, when printing is sprayed, continuous spray works well, and ink phenomenon of breaking is few.
After molding powder provided by the invention and liquid-containing binder printing shaping, obtained ceramic core green body it is anti-
Compressive Strength can achieve 3MPa or more, which can guarantee that ceramic core green body will not be damaged when clearing up powder, convenient to beat
Print the cleaning of powder on apparatus platform.
In above embodiment of the invention, according to parts by weight, the parts by weight of liquid-containing binder for example can be
68 parts, 70 parts, 72 parts, 75 parts, 78 parts, 80 parts, 82 parts, 85 parts, 88 parts or 90 parts;The parts by weight of diluent for example can be
9 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts or 30 parts;The parts by weight of surfactant for example may be used
Think 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts or 2 parts.
In certain embodiments of the present invention, the adhesion component is phosphate dihydrogen aluminum solution;The aluminium dihydrogen phosphate
In solution, the mass content of phosphorus pentoxide is 30~40%, and the mass content of aluminum oxide is 8-13%.It is specific using this
The adhesion component of component can improve the viscosity and surface tension of liquid-containing binder, reach and reduce spray head blocking, disconnected ink when printing
The occurrence of.
In certain embodiments of the present invention, the diluent is phosphoric acid solution, the mass concentration of the phosphoric acid solution
It is 10~20%.Diluent using phosphoric acid solution as adhesion component, it can be ensured that aluminium dihydrogen phosphate is dispersedly more uniform,
Adhesion component is to the binding force uniformity for forming powder after guaranteeing printing.
In certain embodiments of the present invention, the surfactant is neopelex, dodecyl ammonia
Base sodium propionate, dodecyl dimethylene amino sodium diformate or lecithin.
Second aspect, the present invention provides a kind of preparation methods of ceramic core printed material, comprising the following steps:
A) powder I will be obtained after the mixture pelleting of refractory aggregate and reinforcing agent;
B) powder II will be obtained after curing agent and dispersant;
C powder I and powder II) are mixed into sieving and obtain the molding powder.
In preparation method provided by the invention, refractory aggregate and reinforcing agent mixing granulation are first obtained into powder I, by curing agent
Powder II is obtained with dispersant, obtained powder I and powder II are then mixed to get molding powder again.The preparation side
In, refractory aggregate is first mixed with reinforcing agent, comes into full contact with the two, available fire resistance is good, the high powder of compressive resistance.So
Afterwards again with curing agent and dispersant to improve the printability for forming powder.
In certain embodiments of the present invention, the step A) in, after the mixing of refractory aggregate and reinforcing agent, add water
Slurry is prepared, mist projection granulating prepares the powder that grain diameter is 35~75 μm, obtains powder I;Further preferred in the present invention
In embodiment, the step B) in, curing agent and dispersing agent obtain powder II after mixing by the way of grinding;In the present invention
In further preferred embodiment, the step C) in, after powder I and powder II were mixed 200 meshes, obtain described
Form powder.By limit preparation process in mist projection granulating particle partial size and final molding powder partial size, be all for
Make finally obtained molding powder has better rollability, and improves the printability of molding powder, improves printing
Precision and print quality.
On the other hand, the present invention also provides the preparation methods of another ceramic core printed material, including following step
It is rapid:
A) molding powder is prepared using above-mentioned preparation method;
B) liquid-containing binder is obtained after mixing binder, diluent with surfactant.
The printed material obtained using the preparation method, the rollability for forming powder is good, and printing precision is high, particle and particle
Between religion easily bonding.It under the action of the liquid-containing binder of invention, can be adhesively fixed rapidly, there is certain adhesion strength.
In certain embodiments of the present invention, first binder is dissolved in diluent, obtains solution I, then surface is living
Property agent be dissolved in solution I, obtain the liquid-containing binder after 1 μm of partial size > of particle of filtering.
A kind of preparation method of ceramic core provides above-mentioned ceramic core and uses printed material as printing raw material, utilizes 3DP
Technology printing shaping, obtains ceramic core.
After powder for molding provided by the invention and liquid-containing binder printing shaping, ceramic core green body is through 800-1000
The high-temperature bending strength of ceramic core obtained after DEG C baking can reach 8MPa or more, and ceramic core is run in casting use process
Fiery rate is low, and the good permeability of ceramic core, and the surface quality of continuous castings cast is good, and dimensional accuracy is high.
Below in conjunction with embodiment and comparative example, the present invention will be further described in detail.
Embodiment 1
The present embodiment is a kind of ceramic core printed material, including molding powder and liquid-containing binder;Wherein, by weight
Number meter, molding powder includes 89.24 parts of mullite powder, 7.76 parts of biphosphate aluminium powder, 1.5 parts of magnesia and gas phase titanium dioxide
1.5 parts of silicon;Liquid-containing binder include 82.74 parts of aluminium dihydrogen phosphate liquid, mass fraction be 15% 15.76 parts of phosphoric acid solution and
1.5 parts of neopelex.
Wherein, in aluminium dihydrogen phosphate liquid, the mass content of phosphorus pentoxide is 35%, the mass content of aluminum oxide
It is 10%.
The preparation method of ceramic core printed material in the present embodiment, comprising the following steps:
A) mullite powder, biphosphate aluminium powder and 50 parts of distilled water are uniformly mixed, obtain slurry after stirring evenly, using spraying
Pelletizer is granulated, and obtains powder of the diameter between 35~75um, powder I is made after dry;
B) by magnesia and fumed silica after ground and mixed is uniform in drum-type grinding mill, powder II is obtained;
C) by powder I and powder II in three-dimensional material mixer after mixing, with 200 mesh vibration of ultrasonic wave be sieved through filter, obtain
Powder must be formed;
D the concentrated phosphoric acid of mass fraction 85%) is used, the dilute phosphoric acid solution of configuration quality score 15% finally obtains quality point
The phosphoric acid solution that number is 15% obtains diluent;
E aluminium dihydrogen phosphate liquid) is taken, is slowly added in 15.76 parts of diluent, adition process at the uniform velocity stirs molten
Liquid obtains solution I;
F) by neopelex pass into solution I, solution II is obtained;
G nutsch filter) is used, the filter that solution II crosses 1 μm is filtered, liquid-containing binder is obtained.
Embodiment 2
The present embodiment is a kind of ceramic core printed material, including molding powder and liquid-containing binder;Wherein, by weight
Number meter, molding powder includes 90 parts of mullite powder, 5 parts of biphosphate aluminium powder, 2.5 parts of magnesia and fumed silica 2.5
Part;Liquid-containing binder includes 88 parts of aluminium dihydrogen phosphate liquid, 10 parts of phosphoric acid solution and detergent alkylate that mass fraction is 15%
2 parts of sodium sulfonate.
Wherein, in aluminium dihydrogen phosphate liquid, the mass content of phosphorus pentoxide is 35%, the mass content of aluminum oxide
It is 10%.
The ceramic core provided in the preparation method and embodiment 1 of ceramic core printed material in the present embodiment, which is used, to be beaten
The preparation method for printing material is identical.
Embodiment 3
The present embodiment is a kind of ceramic core printed material, including molding powder and liquid-containing binder;Wherein, by weight
Number meter, molding powder includes 86 parts of mullite powder, 10 parts of biphosphate aluminium powder, 2.0 parts of magnesia and fumed silica 2.0
Part;Liquid-containing binder includes 76.8 parts of aluminium dihydrogen phosphate liquid, 22 parts of phosphoric acid solution and dodecyl that mass fraction is 15%
1.2 parts of benzene sulfonic acid sodium salt.
Wherein, in aluminium dihydrogen phosphate liquid, the mass content of phosphorus pentoxide is 35%, the mass content of aluminum oxide
It is 10%.
The ceramic core provided in the preparation method and embodiment 1 of ceramic core printed material in the present embodiment, which is used, to be beaten
The preparation method for printing material is identical.
Embodiment 4
The present embodiment is a kind of ceramic core printed material, difference from example 1 is that, biphosphate molten aluminum
In body, the mass content of phosphorus pentoxide is 50%, and the mass content of aluminum oxide is 5%.
The ceramic core provided in the preparation method and embodiment 1 of ceramic core printed material in the present embodiment, which is used, to be beaten
The preparation method for printing material is identical.
Embodiment 5
The present embodiment is a kind of ceramic core printed material, including molding powder and liquid-containing binder;Wherein, by weight
Number meter, molding powder include 90 parts of schmigel, 5 parts of sodium metasilicate, 2.5 parts of copper oxide and 2.5 parts of stearic acid;Liquid-containing binder packet
88 parts of aluminium dihydrogen phosphate liquid, mass fraction are included as 15% 10 parts of phosphoric acid solution and 2 parts of sodium dodecyl aminopropionitrile.
Wherein, in aluminium dihydrogen phosphate liquid, the mass content of phosphorus pentoxide is 35%, the mass content of aluminum oxide
It is 10%.
The ceramic core provided in the preparation method and embodiment 1 of ceramic core printed material in the present embodiment, which is used, to be beaten
The preparation method for printing material is identical.
Embodiment 6
The present embodiment is a kind of ceramic core printed material, and the composition of powder and liquid-containing binder is formed in the present embodiment
Ingredient is same as Example 1, the difference is that the preparation method in the present embodiment is different from embodiment 1.
The preparation method of ceramic core printed material in the present embodiment, comprising the following steps:
A) mullite powder, biphosphate aluminium powder and 50 parts of distilled water are uniformly mixed, obtain slurry after stirring evenly, using spraying
Pelletizer is granulated, and obtains powder of the diameter between 20~35um, powder I is made after dry;
B) by magnesia and fumed silica after ground and mixed is uniform in drum-type grinding mill, powder II is obtained;
C) by powder I and powder II in three-dimensional material mixer after mixing, with 300 mesh vibration of ultrasonic wave be sieved through filter, obtain
Powder must be formed;
D the concentrated phosphoric acid of mass fraction 85%) is used, the dilute phosphoric acid solution of configuration quality score 15% finally obtains quality point
The phosphoric acid solution that number is 15% obtains diluent;
E aluminium dihydrogen phosphate liquid) is taken, is slowly added in 15.76 parts of diluent, adition process at the uniform velocity stirs molten
Liquid obtains solution I;
F) by neopelex pass into solution I, solution II is obtained;
G nutsch filter) is used, the filter that solution II crosses 1 μm is filtered, liquid-containing binder is obtained.
Embodiment 7
The present embodiment is a kind of ceramic core printed material, and the composition of powder and liquid-containing binder is formed in the present embodiment
Ingredient is same as Example 1, the difference is that the preparation method in the present embodiment is different from embodiment 1.
The preparation method of ceramic core printed material in the present embodiment, comprising the following steps:
A) mullite powder, biphosphate aluminium powder and 50 parts of distilled water are uniformly mixed, obtain slurry after stirring evenly, using spraying
Pelletizer is granulated, and obtains powder of the diameter between 75~110um, powder I is made after dry;
B) by magnesia and fumed silica after ground and mixed is uniform in drum-type grinding mill, powder II is obtained;
C) by powder I and powder II in three-dimensional material mixer after mixing, with 400 mesh vibration of ultrasonic wave be sieved through filter, obtain
Powder must be formed;
D the concentrated phosphoric acid of mass fraction 85%) is used, the dilute phosphoric acid solution of configuration quality score 15% finally obtains quality point
The phosphoric acid solution that number is 15% obtains diluent;
E aluminium dihydrogen phosphate liquid) is taken, is slowly added in 15.76 parts of diluent, adition process at the uniform velocity stirs molten
Liquid obtains solution I;
F) by neopelex pass into solution I, solution II is obtained;
G nutsch filter) is used, the filter that solution II crosses 1 μm is filtered, liquid-containing binder is obtained.
Comparative example 1
This comparative example is a kind of ceramic core printed material, including molding powder and liquid-containing binder;Wherein, by weight
Number meter, molding powder includes 96 parts of mullite powder, 3 parts of biphosphate aluminium powder, 0.5 part of magnesia and fumed silica 0.5
Part;Liquid-containing binder includes 50 parts of adhesion component, 40 parts of diluent and 10 parts of surfactant.
Wherein, in aluminium dihydrogen phosphate liquid, the mass content of phosphorus pentoxide is 35%, the mass content of aluminum oxide
It is 10%.
Preparation method in this comparative example in the preparation method with embodiment 1 of ceramic core printed material is identical.
Comparative example 2
This comparative example is a kind of preparation method of ceramic core, and the preparation method is using the hydrolyzate of silester as viscous
Agent is tied, after being made into slurry with refractory material mullite powder, is fired using mold by techniques such as grouting, gum deposit, molding, roastings
At.
The ceramic core for being utilized respectively embodiment 1-7 and the offer of comparative example 1 prints ceramic core with printed material, and record is beaten
The problems in print process, and the ceramic core obtained after the test printing obtained compression strength and baking of ceramic core green body
High-temperature bending strength at flexural strength and 900 DEG C, the ceramic core then provided with comparative example 2 compare.As a result it is listed in
Table 1.
1 comparing result of table
It can be seen that ceramic core powder in printed material print procedure that embodiment 1-7 is provided from the data in table 1
It is laid with uniformly, ink emission rate >=95%, and prints the pottery obtained after the compression strength and baking of obtained ceramic core green body
High-temperature bending strength at the flexural strength and 900 DEG C of porcelain type core illustrates this obviously higher than the printed material in comparative example 1
Ceramic core has a significant impact the performance of printed material with the ingredient of constitutive material each in printed material, only mentions in the present invention
Within the scope of the raw material proportioning of confession, the excellent printed material of properties can be just prepared.Compared with comparative example 2, the present invention is utilized
The printed material printing ceramic core of offer can significantly reduce product manufacturing cycle.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from of the invention
Many other change and modification can be made in the case where spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.