CN107445627A - A kind of preparation method of phenolic resin and manganese dioxide bilayer film coated ceramic powder - Google Patents

A kind of preparation method of phenolic resin and manganese dioxide bilayer film coated ceramic powder Download PDF

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CN107445627A
CN107445627A CN201710731487.4A CN201710731487A CN107445627A CN 107445627 A CN107445627 A CN 107445627A CN 201710731487 A CN201710731487 A CN 201710731487A CN 107445627 A CN107445627 A CN 107445627A
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ceramic
phenolic resin
preparation
powder
ceramic powders
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CN107445627B (en
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吴甲民
陈敬炎
史玉升
刘荣臻
陈安南
文世峰
李晨辉
贺智勇
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Beijing Cisri-Nmt Advanced Materials & Technology Co Ltd
Huazhong University of Science and Technology
Shenzhen Huazhong University of Science and Technology Research Institute
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Beijing Cisri-Nmt Advanced Materials & Technology Co Ltd
Huazhong University of Science and Technology
Shenzhen Huazhong University of Science and Technology Research Institute
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Abstract

The invention belongs to rapid shaping technique field, and in particular to a kind of preparation method of phenolic resin and manganese dioxide bilayer film coated ceramic powder, comprise the following steps：(1) potassium permanganate is added in deionized water and is made into homogeneous phase solution, and ceramic powders are uniformly distributed in homogeneous phase solution；(2) acetic acid manganese solution is instilled into mixed solution, filters, dry and sieves, obtain MnO2The ceramic powders of cladding；(3) by MnO2Ceramic powders and the phenolic resin mixing of cladding, add enough alcohol solvents, rotary evaporation to a small amount of ethanol, and (4) take out composite powder, dry, grind and sieve, that is, obtain phenolic resin and manganese dioxide bilayer film coated ceramic powder.Present invention process is simple, and overlay film effect is good and low for equipment requirements, and efficiently solving sintering aid, skewness, binding agent the problems such as skewness, can be effectively improved the sintering character and mechanical property of ceramic part in ceramic powder in the base.

Description

A kind of preparation method of phenolic resin and manganese dioxide bilayer film coated ceramic powder
Technical field
The invention belongs to rapid shaping technique field, is covered more particularly, to a kind of phenolic resin and manganese dioxide bilayer The preparation method of film ceramic powders, it can solve the problem that sintering aid, and skewness, binding agent divide in ceramic powder in the base The problems such as cloth is uneven.
Background technology
Selective laser sintering is that one kind drives direct manufacturing parts based on " discrete-accumulation " forming principle, by three-dimensional data Method.Compared with classical production process, SLS technologies have design freedom high, and the research and development of products cycle is short and manufacturing cost is low , can be without rapid mould labyrinth ceramic part etc. advantage.Due to ceramics sintering temperature is higher and ceramic powder Bulk density is limited, it is difficult to using the direct sinter molding ceramic component of laser, low melting point need to be typically introduced in ceramic powder High polymer material, ceramics/macromolecule composite powder is carried out optionally according to the data of each layer cross section under the control of the computer Laser scanning sinters, and high polymer material is melted and then is bonded ceramic particle, is successively molded, obtains ceramic body, then Various ceramic parts are prepared by postprocessing working procedures such as dumping, sintering.
The hybrid mode of ceramic powders and high polymer binder mainly has two kinds.1. mechanical mixing：By ceramic powders with Polymeric powder is directly mixed in planetary ball mill or three-dimensional rolling powder machine by a certain percentage, is prepared and is suitable to SLS shapings The shortcomings that composite powder, this powder mode processed have the advantages of technique is simple, but its is maximum is that binding agent is difficult to be uniformly distributed, So as to influence the SLS Forming Qualities of binding agent/ceramic composite powder.2. method with plastic film：Macromolecule is bonded by certain mode Agent is evenly coated on ceramic grain surface.It is multiple that this powder mode processed can obtain the equally distributed binding agent/ceramics of binding agent Powder is closed, is advantageous to improve the SLS Forming Qualities of binding agent/ceramic composite powder.However, currently used film mulching method is as sprayed Mist comminution granulation and dissolving precipitated method are higher to equipment requirement, and technological process is complicated and cost is higher.
Although led in addition, preparing the Advanced Ceramic Components with labyrinth using selective laser sintering technology in industry The great application prospect in domain, however, the introducing of the sintering of such ceramic part, microstructure and performance and sintering aid and its point Cloth also has close relationship.At present, sintering aid is typically all and is introduced directly into by mechanical mixing, although this mode is grasped Make simply, but because granularity and the difference of powder density can cause sintering aid skewness in the base, it is multiple so as to reduce Close the sintering character of powder and the final mechanical property for influenceing ceramic part.
Due to drawbacks described above and deficiency be present, this area is needed badly to make and further improved, and designs a kind of ceramics The preparation method of powder, can avoiding sintering aid, skewness, binding agent are distributed not in ceramic powder in the base The problem of uniform.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the invention provides a kind of phenolic resin and manganese dioxide are double The preparation method of layer film coated ceramic powder, wherein by being designed to being used as the crucial raw material components for participating in thing and proportioning, phase It should research and propose and take full advantage of chemical coprecipitation and uniformly adhere to a thin layer MnO on ceramic powders surface2Sintering aid, then Phenolic resin adhesive is coated on to the principle on its surface, phenolic resin and manganese dioxide bilayer polymer-coated ceramic powder are formed for processing Powder；Targeted design additionally is carried out to the important technical parameter of subsequent technique, accordingly can preferably solve sintering aid in base Skewness, binding agent the problems such as skewness, can be effectively improved the agglutinating property of ceramic part in ceramic powder in body Can and mechanical property, while exist high efficiency, high quality, cost it is low and be easy to manipulation the advantages that, be therefore particularly suitable for laser The MnO of the phenolic resin cladding of constituency sintering2The preparation of/ceramic composite powder.
To achieve the above object, the invention provides the system of a kind of phenolic resin and manganese dioxide bilayer film coated ceramic powder Preparation Method, it is characterised in that specifically comprise the following steps：
(1) potassium permanganate is added in deionized water and is made into homogeneous phase solution, be then added to ceramic powders above-mentioned equal In phase solution, stirring makes ceramic powders be evenly distributed, wherein, the mass ratio of ceramic powders and deionized water is 1:(1-5)；
(2) acetic acid manganese solution is slowly instilled into mixed solution while stirring, continues to stir, then filter mixed liquor, Drying and sieving, obtain MnO2The ceramic powders of cladding；
(3) by obtained MnO2The ceramic powders of cladding mix with phenolic resin, and add alcohol solvent, while stirring Heating water bath is carried out, ethanol evaporation is obtained composite powder；
(4) composite powder after ethanol evaporation is taken out, sieving is ground after drying, that is, obtains phenolic resin and manganese dioxide is double Layer film coated ceramic powder.
Specifically, the present invention uniformly adheres to a thin layer MnO using chemical coprecipitation in ceramic grain surface2Sintering aid； Then phenolic resin is uniformly wrapped on by MnO using solvent evaporated method2On the ceramic grain surface of sintering aid cladding, it can solve the problem that Skewness, binding agent the problems such as skewness, can be effectively improved ceramics zero to sintering aid in ceramic powder in the base The sintering character and mechanical property of part.
It is further preferred that the ceramic powders described in step (1) are oxide, carbide, nitride or aluminosilicate One or more.
Preferably, the ceramic powder described in step (1) is shaped as spherical or irregular shape, and its grain size scope is Asia Micron order, micron order, and grain size is no more than 200 μm.
The species of above-mentioned ceramic powders is applied to selective laser sintering, and the cheap easily acquisition of cost, by its shape and size Control within the above range, can ensure that its sintering character and mechanical property are preferable, be advantageous to sizing during selective laser sintering.
Preferably, in step (2), the follow-up continuous stirring 0.5h~6h of acetic acid manganese solution, and described acetic acid manganese solution are added Concentration ratio with liquor potassic permanganate is 3:2.By the Ratio control of acetic acid manganese solution and liquor potassic permanganate in above range, energy Enough ensure that reaction is smoothed out, ceramic powders surface is uniformly coated enough MnO2Sintering aid, be advantageous to sintering process The mass transfer of middle ceramic part internal particle and the progress reset, improve its sintering character and mechanical property.
Preferably, the drying temperature described in step (2) is 40 DEG C~80 DEG C, and drying time is 4h~24h.
Preferably, in step (3), the content of described phenolic resin is 10wt%~40wt% of composite powder.By phenol The content of urea formaldehyde is controlled in above range, then ceramic powders surface can be enable uniformly to coat enough phenolic resin, had Beneficial to the Forming Quality for improving biscuit of ceramics, so as to improve the performance of final ceramic part.
Preferably, for step (3) by the way of rotary evaporation, bath temperature is arranged to 30 DEG C~60 DEG C.
Preferably, the drying temperature described in step (4) is 40 DEG C~60 DEG C, and drying time is 6h~24h.
Specifically, the parameter of the processing steps such as follow-up drying, water-bath and drying is defined, reaction can be ensured It is smoothed out, obtains double-contracting of good performance and cover ceramic powders, solving sintering aid, skewness, binding agent is being made pottery in the base In porcelain powder the problems such as skewness.
In general, by the contemplated above technical scheme of the present invention compared with prior art, have advantages below and Beneficial effect：
(1) present invention is to being used as the crucial raw material components for participating in thing and proportioning by being designed, accordingly research and propose and Take full advantage of chemical coprecipitation and uniformly adhere to a thin layer MnO on ceramic powders surface2Sintering aid, then by phenolic resin bag The principle on its surface is overlayed on, phenolic resin and manganese dioxide bilayer film coated ceramic powder are formed for processing；Additionally to follow-up The important technical parameter of technique carries out targeted design, accordingly can preferably solve sintering aid skewness, viscous in the base Knot agent the problems such as skewness, can be effectively improved the sintering character and mechanical property of ceramic part, simultaneously in ceramic powder It is low and the advantages that be easy to manipulation to there is high efficiency, high quality, cost, is therefore particularly suitable for the phenolic resin of selective laser sintering The MnO of cladding2The preparation of/ceramic composite powder.
(2) present invention prepares MnO using chemical coprecipitation2The composite powder of sintering aid coating ceramic, can effectively solve MnO2Situation pockety in the base, the present invention add MnO into ceramic powders2Sintering aid, be advantageous in sintering process The mass transfer of ceramic part internal particle and the progress reset, so as to improve the sintering character of ceramic part and mechanical property.
(3) phenolic resin is evenly coated at MnO by the present invention using solvent evaporated method2, can on/ceramic composite powder surface Effectively solve the problems, such as binding agent skewness in ceramic powder, be advantageous to improve the Forming Quality of biscuit of ceramics, so as to Improve the performance of final ceramic part.Traditional film mulching method such as spray granulation is also solved, dissolving precipitated method is to equipment requirement Higher, the problems such as complex process and cost are larger.
(4) species for the ceramic powders that present invention choosing limits is applied to selective laser sintering, and the cheap easily acquisition of cost, and By the control of its shape and size within the above range, and to the parameter of the processing steps such as follow-up drying, water-bath and drying carry out Limit, being smoothed out for reaction can be ensured, obtain double-contracting of good performance and cover ceramic powders, solve sintering aid and divide in the base Cloth is uneven, binding agent is in ceramic powder the problems such as skewness.
Brief description of the drawings
Fig. 1 is the flow chart of the preparation method of phenolic resin and manganese dioxide bilayer film coated ceramic powder of the present invention.
Fig. 2 (a) and (b) are MnO in embodiment 12Coat the SEM figures and EDS figures of the composite powder of mullite；
Fig. 3 (a) and (b) are that phenolic resin coats MnO in embodiment 12The SEM figures and EDS figures of/mullite composite powder.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and It is not used in the restriction present invention.As long as in addition, technical characteristic involved in each embodiment of invention described below Conflict can is not formed each other to be mutually combined.
The invention provides the preparation method of a kind of phenolic resin and manganese dioxide bilayer film coated ceramic powder, headed by specific A thin layer MnO is uniformly first adhered in ceramic grain surface using chemical coprecipitation2Sintering aid；Then, using solvent evaporated method Phenolic resin is uniformly wrapped on MnO2On the ceramic grain surface of sintering aid cladding.This method technological process is simple, is easy to grasp Work, universality are strong, and solving sintering aid, skewness, binding agent skewness etc. in ceramic powder are asked in the base Topic, the sintering character and mechanical property of ceramic part can be effectively improved.
The preparation method of the present invention mainly comprises the following steps：
(1) potassium permanganate is added in deionized water and is made into homogeneous phase solution, then, ceramic powders are added to permanganic acid Mechanical agitation is carried out in potassium homogeneous phase solution, wherein, the mass ratio of ceramic powders and deionized water is 1：1~1：5, make ceramic powders It is uniformly distributed in solution；
Above-mentioned ceramic powders species includes the one or more of oxide, carbide, nitride or aluminosilicate, its particle diameter Size range should be submicron order, micron order, but grain size is not to be exceeded 200 μm；Ceramic particle shape can be spherical or not Regular shape；
(2) acetic acid manganese solution is slowly instilled into mixed solution while stirring, continues to stir 0.5h~6h, then will mixing Liquid filters, dries and sieved, and obtains MnO2The composite powder of coating ceramic；
The concentration ratio of acetic acid manganese solution and liquor potassic permanganate is preferably 3:2；Drying temperature is preferably 40 DEG C~80 DEG C, is done The dry time is preferably 4h~24h；
(3) MnO that will be prepared in step (2)2The ratio input rotation needed for of the ceramic powders and phenolic resin of cladding is steamed Send out in device, add enough alcohol solvents, bath temperature is arranged to 30 DEG C~60 DEG C while mechanical agitation；
(4) composite powder is taken out during rotary evaporation to a small amount of alcohol, is put into drying box and dries, finally by composite powder Grinding sieving, that is, obtain the MnO coated suitable for the phenolic resin of selective laser sintering2/ ceramic composite powder；
Wherein, the content of phenolic resin is preferably 10wt%~40wt%；Drying temperature is preferably 40 DEG C~60 DEG C, is dried Time is preferably 6h~24h.
Preferably to explain the present invention, several specific embodiments given below：
Embodiment 1
31.6g potassium permanganate is dissolved in 200mL deionized waters, configures 1mol/L liquor potassic permanganate；Then, will 200g average grain diameters are 15 μm, mullite ceramic powder in irregular shape is added in liquor potassic permanganate, in 400r/min Stir speed (S.S.) under stir 0.5h, then, be slowly dropped into mixed solution 30mL concentration be 1.5mol/L acetic acid manganese solution, Continue to stir 0.5h；Finally mixed solution is filtered 4 times, 40 DEG C of drying 24h, 200 mesh sieves is crossed, obtains MnO2Coat mullite Composite powder；If Fig. 2 (a) and (b) are MnO in the embodiment 12Coat the SEM figures and EDS figures of the composite powder of mullite；
By MnO2Ceramic powders, the phenolic resin in mass ratio 85 of cladding:In 15 input rotary evaporators, add enough Alcohol solvent, bath temperature is arranged to 50 DEG C while mechanical agitation, being taken out when alcohol content is in 18wt% or so should Composite powder, by composite powder 60 DEG C of drying 6h, ground 200 mesh sieves, obtain the phenolic resin suitable for selective laser sintering The MnO of cladding2/ mullite composite powder.The composite powder be shaped as it is subsphaeroidal, average grain diameter be 50 μm.Such as Fig. 3 (a) and (b) It is that phenolic resin coats MnO in the embodiment 12The SEM figures and EDS figures of/mullite composite powder.
Embodiment 2
31.6g potassium permanganate is dissolved in 200mL deionized waters, configures 1mol/L liquor potassic permanganate；Then, will The alumina ceramic powder that 200g average grain diameters are 0.8 μm, shape is subsphaeroidal is added in liquor potassic permanganate, in 400r/min Stir speed (S.S.) under stir 0.5h, then, be slowly dropped into mixed solution 18mL concentration be 1.5mol/L acetic acid manganese solution, Continue to stir 6h；Finally mixed solution is filtered 4 times, 70 DEG C of drying 8h, 200 mesh sieves is crossed, obtains MnO2Coated aluminum oxide is answered Close powder；
By MnO2Ceramic powders, the phenolic resin in mass ratio 60 of cladding:In 40 input rotary evaporators, add enough Alcohol solvent, bath temperature is arranged to 30 DEG C while mechanical agitation, being taken out when alcohol content is in 18wt% or so should Composite powder, by composite powder 50 DEG C of drying 8h, ground 200 mesh sieves, obtain the phenolic resin suitable for selective laser sintering The MnO of cladding2/ alumina composite powder.The composite powder be shaped as it is subsphaeroidal, average grain diameter be 25 μm.
Embodiment 3
158g potassium permanganate is dissolved in 1000mL deionized waters, configures 1mol/L liquor potassic permanganate；Then, will 200g average grain diameters are 45 μm, are shaped as subsphaeroidal silicon nitride ceramic powder and are added in liquor potassic permanganate, in 400r/ 0.5h is stirred under min stir speed (S.S.), then, the manganese acetate that 192mL concentration is 1.5mol/L is slowly dropped into mixed solution Solution, continue to stir 3h；Finally mixed solution is filtered 4 times, 80 DEG C of drying 4h, 200 mesh sieves is crossed, obtains MnO2Coat silicon nitride Composite powder；
By MnO2Ceramic powders, the phenolic resin in mass ratio 90 of cladding:In 10 input rotary evaporators, add enough Alcohol solvent, bath temperature is arranged to 60 DEG C while mechanical agitation, being taken out when alcohol content is in 18wt% or so should Composite powder, by composite powder 40 DEG C of drying 24h, ground 200 mesh sieves, obtain the phenolic resin suitable for selective laser sintering The MnO of cladding2/ silicon nitride composite powder.The composite powder be shaped as it is subsphaeroidal, average grain diameter be 60 μm.
Embodiment 4
94.8g potassium permanganate is dissolved in 600mL deionized waters, configures 1mol/L liquor potassic permanganate；Then, will 200g average grain diameters are 50 μm, cordierite ceramic powder in irregular shape is added in liquor potassic permanganate, in 400r/min Stir speed (S.S.) under stir 0.5h, then, be slowly dropped into mixed solution 90mL concentration be 1.5mol/L acetic acid manganese solution, Continue to stir 2h；Finally mixed solution is filtered 4 times, 70 DEG C of drying 8h, 200 mesh sieves is crossed, obtains MnO2Cladding cordierite is answered Close powder；
By MnO2Ceramic powders, the phenolic resin in mass ratio 85 of cladding:In 15 input rotary evaporators, add enough Alcohol solvent, bath temperature is arranged to 50 DEG C while mechanical agitation, being taken out when alcohol content is in 18wt% or so should Composite powder, by composite powder 60 DEG C of drying 6h, ground 200 mesh sieves, obtain the phenolic resin suitable for selective laser sintering The MnO of cladding2/ cordierite composite powder, the composite powder be shaped as it is subsphaeroidal, average grain diameter be 75 μm.
Embodiment 5
31.6g potassium permanganate is dissolved in 200mL deionized waters, configures 1mol/L liquor potassic permanganate；Then, will The silicon carbide ceramics powder that 200g average grain diameters are 20 μm, shape is subsphaeroidal is added in liquor potassic permanganate, in 400r/min Stir speed (S.S.) under stir 0.5h, then, be slowly dropped into mixed solution 6mL concentration be 1.5mol/L acetic acid manganese solution, Continue to stir 3h；Finally mixed solution is filtered 4 times, 60 DEG C of drying 16h, 200 mesh sieves is crossed, obtains MnO2Cladding carborundum is answered Close powder；
By MnO2Ceramic powders, the phenolic resin in mass ratio 85 of cladding:In 15 input rotary evaporators, add enough Alcohol solvent, bath temperature is arranged to 50 DEG C while mechanical agitation, being taken out when alcohol content is in 18wt% or so should Composite powder, by composite powder 55 DEG C of drying 6h, ground 200 mesh sieves, obtain the phenolic resin suitable for selective laser sintering The MnO of cladding2/ silicon carbide compound powder.The composite powder be shaped as it is subsphaeroidal, average grain diameter be 45 μm.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to The limitation present invention, all any modification, equivalent and improvement made within the spirit and principles of the invention etc., all should be included Within protection scope of the present invention.

Claims (8)

  1. A kind of 1. preparation method of phenolic resin and manganese dioxide bilayer film coated ceramic powder, it is characterised in that specifically include as Lower step：
    (1) potassium permanganate is added in deionized water and is made into homogeneous phase solution, then ceramic powders are added to and above-mentioned mixed In liquid, stirring makes ceramic powders be evenly distributed, wherein, the mass ratio of ceramic powders and deionized water is 1:(1-5)；
    (2) acetic acid manganese solution is slowly instilled into mixed solution while stirring, continues to stir, then mixed liquor is filtered, dried And sieving, obtain MnO2The ceramic powders of cladding；
    (3) by obtained MnO2The ceramic powders of cladding mix with phenolic resin, and add alcohol solvent, carry out while stirring Heating water bath, ethanol evaporation is set to obtain composite powder；
    (4) composite powder after ethanol evaporation is taken out, sieving is ground after drying, that is, obtains phenolic resin and manganese dioxide bilayer covers Film ceramic powders.
  2. 2. preparation method as claimed in claim 1, it is characterised in that the ceramic powders described in step (1) are oxide, carbon The one or more of compound, nitride or aluminosilicate.
  3. 3. preparation method as claimed in claim 1 or 2, it is characterised in that the ceramic powder described in step (1) is shaped as spherical Or irregular shape, its grain size scope are that submicron order, micron order, and grain size are no more than 200 μm.
  4. 4. preparation method as claimed in claim 3, it is characterised in that in step (2), add the follow-up continuous stirring of acetic acid manganese solution 0.5h~6h, and the concentration ratio of described acetic acid manganese solution and liquor potassic permanganate is 3:2.
  5. 5. preparation method as claimed in claim 4, it is characterised in that the drying temperature described in step (2) is 40 DEG C~80 DEG C, drying time is 4h~24h.
  6. 6. preparation method as claimed in claim 5, it is characterised in that in step (3), the content of described phenolic resin is multiple Close 10wt%~40wt% of powder.
  7. 7. preparation method as claimed in claim 6, it is characterised in that step (3) is by the way of rotary evaporation, bath temperature It is arranged to 30 DEG C~60 DEG C.
  8. 8. preparation method as claimed in claim 7, it is characterised in that the drying temperature described in step (4) is 40 DEG C~60 DEG C, drying time is 6h~24h.
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CN114220956A (en) * 2021-12-06 2022-03-22 厦门理工学院 Si @ MnO @ C composite material, preparation method thereof, negative electrode material and battery

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