CN108676166A - Light sensitive ceramics forerunner's preparation of ceramic product is manufactured for increases material manufacturing technology - Google Patents
Light sensitive ceramics forerunner's preparation of ceramic product is manufactured for increases material manufacturing technology Download PDFInfo
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- CN108676166A CN108676166A CN201810724474.9A CN201810724474A CN108676166A CN 108676166 A CN108676166 A CN 108676166A CN 201810724474 A CN201810724474 A CN 201810724474A CN 108676166 A CN108676166 A CN 108676166A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
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Abstract
The invention discloses a kind of light sensitive ceramics forerunner's preparations manufacturing ceramic product for increases material manufacturing technology, include the following steps：Chloromethylmethyldichlorsilane obtains linear polysiloxane with dichloromethyl vinyl silanes hydrolysis, then dimethyl vinyl chlorosilane is used to carry out end capping reaction to linear polysiloxane, the polysiloxanes after sealing end obtains light sensitive ceramics presoma with 2 hydroxyl ethyl ester of acrylic acid, triethylamine react.The present invention prepares the polysiloxanes ceramic forerunner of uV curable, gained light sensitive ceramics presoma is under the addition for being suitble to initiator, it can reach 80% double bond conversion rate when ultraviolet light 30s, when 40s can reach 90% double bond conversion rate, have very efficient light-cured performance；It regard the light sensitive ceramics presoma of the present invention as raw material, using stereo lithography progress increasing material manufacturing, the cured article of regular appearance can be obtained, the cured article smooth appearance, intensity is higher.
Description
Technical field
The invention belongs to ceramic material increases material manufacturing technology fields, and in particular to one kind is for increases material manufacturing technology manufacture pottery
Light sensitive ceramics forerunner's preparation of porcelain products.
Background technology
With metal and polymer phase ratio, ceramics are difficult to, and are especially machined to complicated shape.Ceramics have very high melt
Point and hardness, but toughness is poor, and this so that ceramics are difficult to be processed by way of casting or cutting.Traditional ceramics are processed
Typically by ceramic powders be sintered or by ceramics deposition cure in the film, in this process the generation of defect be can not
It avoids, if the compactness and homogeneity of hole and inhomogeneities, and ceramics are to determine the key factor of ceramic performance, therefore,
Such processing method is difficult to obtain ceramic product of good performance.
Ceramics, which are difficult to be processed, limits utilization to ceramic excellent performance, such as high temperature resistant, environmental stability and high-strength
Degree etc..In recent years, as increases material manufacturing technology is in the continuous breakthrough of field of ceramic processing, a variety of forming methods have been employed successfully in
Manufacture ceramic product.Traditional ceramics material structure manufacturing mode has been overturned in the appearance of increases material manufacturing technology, in labyrinth function
Being integrated reduces cost and shortens lead time etc. great potential, causes volume widely to be paid close attention in worldwide
And attention, printing shaping technique such as fusion sediment ceramics molding (FDM), the laser of a variety of suitable ceramic parts have been developed at present
Constituency sinter molding (SLS/SLM), the stereolithography (SLA) of UV curing photosensitive resin base ceramic slurry, hot pressing are viscous
Connect the laminated solid body molding (LOM) of ceramic membrane material, 3 D-printing molding (3DP) of organic binder bonded ceramics powder etc.
Technique, and prodigious progress is achieved in terms of material molding.But it is currently used for the increases material manufacturing technology of ceramic material
It is all based on the successively stacked system of ceramic powders, and available ceramic powder material composition is extremely limited.Maturation can quotient at present
Ceramic material 3D printing system is seldom, prints the following two modes of principle generally use：1, the solidification based on selectivity
Photosensitive resin containing ceramic particle；2, by ceramic particle in air can quick-setting liquid-containing binder mix,
It is selectively deposited on workbench by spout again；3, ceramic powder surface is coated into one layer of thermoplastic organics, is selected with laser
The surface sweeping powder bed of selecting property makes scaned surface region ceramic powder outer layer organic matter melt, to which scanning area to be bonded together.Institute
There are these technologies since it is desired that removal binder, overall processing process is time-consuming and laborious, and is all based on ceramic powders, hole
Gap, inhomogeneities are the problem of can not avoiding, and the addition of binder introduces prodigious thermal gradient, and are difficult to go completely
It removes, this makes the decomposition because of binder in sintering process will produce a large amount of crack, and escaping gas can also further expand
Ceramic internal flaw, it is difficult to have very high intensity and reliability that these problems, which directly result in final ceramic product,.
In recent years, a kind of new ceramics increases material manufacturing technology, that is, be based on polymer precursor ceramic material and cubic light is solid
The increases material manufacturing technology for changing moulding process causes extensive concern, because it has avoided the above problem well, can obtain high property
The ceramics printing product of energy.
Polymer precursor ceramics (Polymer Derived Ceramics, PDCs) are with silicon substrate high-molecular organic material
It is obtained after Pintsch process for presoma, such as polysilane, Polycarbosilane, polysiloxanes, polysilazane, PVDF hollow fiber membrane
Inorganic amorphous ceramics, Si-C-N, Si-O-C are most important two systems in PDCs, on the basis of the two ternary systems
On, other elements (B, Al, Ti, Zr, Hf etc.) can be further introduced into, to improve the performance of ceramic some aspects.With common pottery
Porcelain is compared, and PDCs has the advantage that：
1. technical process is easy, quick, preparation temperature is low, burning is helped to the harmful oxide of mechanical behavior under high temperature not adding
In the case of tying agent, it can be prepared at 1000 DEG C or so, therefore fault in material is minimized, at low cost.
2. different by starting material of powder from other ceramic sinterings, the raw material for preparing PDCs is liquid polymer and can lead to
Chemical method is crossed with ultraviolet light sensitive characteristic, therefore macromolecule technique processing various parts can be used for reference, particularly suitable for manufacture
The ceramic component of complicated shape.
3. although PDC ceramics are synthesized in lower temperature, fabulous high-temperature stability, high-temperature creep resistance, oxygen are but shown
The property changed and corrosion resistance, amorphous state can be kept using the amorphous Si CN ceramics that polysilazane is obtained as precursor in an inert atmosphere
To 1500C, creep-resistant property is substantially better than polycrystalline Si C and Si3N4；B is added in SiCN, the quaternary SiBCN ceramics of acquisition have
More preferably resistance to high temperature oxidation and corrosive power (2000C) are particularly suitable for using in high-temperature severe environment.Heat resistanceheat resistant excellent PDCs
Also more adaptive vector spout deflection air-flow impacts the high-speed high-strength of component to impact.
4. ceramic reinforcing material is mixed on accurate micro-scale in the design of atomic scale by polymer precursor,
The ingredient of PDC ceramics even atom/nanostructure can be controlled, and manufacture ceramic matric composite is make it especially suitable for.
That is PDCs can by design presoma be formed with changing product, structure, property, meet individual material properties requirement.
2015,《Science》On delivered current research of the U.S. laboratories HRL in terms of ceramic increasing material manufacturing at
Fruit.They are exactly to print biscuit of ceramics using SLA techniques, then annealed conversion using polymer precursor as primary raw material
At fine and close SiOC ceramic components.This material and technology can produce especially complex ceramic component, and researcher utilizes
Electron microscope analyzes final products, and hole and crackle are not detected on its surface.Further test is found
The ceramic material can withstand up to 1400 DEG C of high temperature without cracking and shrinking.Researcher thinks, this superpower, high temperature resistant
Ceramics be expected to be used for manufacture jet engine and the heavy parts on supersonic plane, the complex component in MEMS etc.
Numerous areas.
In conclusion PDCs liquid photosensitive resins presoma and Stereolithography technique are perfectly combined, PDCs is added
Excellent high-temperature behavior makes this increases material manufacturing technology have unique advantage in special precision ceramic component processing.
Invention content
The purpose of the present invention is intended to overcome the shortcoming of existing method, provides a kind of for increases material manufacturing technology manufacture
Light sensitive ceramics forerunner's preparation of ceramic product is added using light sensitive ceramics presoma obtained by this method in suitable initiator
Under entering, there is efficient light-cured performance.
In order to achieve the above object, the present invention provides a kind of photosensitive potteries manufacturing ceramic product for increases material manufacturing technology
Porcelain forerunner's preparation, synthetic route are as follows：
In formula, n is positive integer；
Specific synthetic method is as follows：
Step 1, as shown in formula (I), under protection of argon gas, successively by chloromethylmethyldichlorsilane and dichloromethyl ethylene
Base silane is added in dry Schllenk bottles, is stirred evenly, and is then added dropwise deionized water thereto, rate of addition be 1 drop/
10s reacts after being added dropwise to bubble-free and generates, obtains reaction solution one at room temperature；Reaction solution one is placed at 45 DEG C and is reacted
12h, reaction finish to obtain linear polysiloxane；
It is charged with dimethyl vinyl chlorosilane after linear polysiloxane is dried and carries out end capping reaction, end capping reaction
Terminated polysiloxane is obtained after 6h；
Wherein, chloromethylmethyldichlorsilane, dichloromethyl vinyl silanes, deionized water：Dimethyl ethenyl chlorine silicon
The volume ratio of alkane is 38.98：40.40：10：3；
Step 2, the terminated polysiloxane that step 1 obtains is placed in ice bath, and is added and seals into terminated polysiloxane
Then the THF for holding polysiloxanes isometric is charged with acrylic acid -2- hydroxyl ethyl esters, stirs evenly, then thereto as solvent
Triethylamine is added dropwise, rate of addition is 1 drop/5s, reacts 4h after being added dropwise in ice bath, obtains reaction solution two after completion of the reaction,
Reaction solution two is filtered, filtrate is collected, then filtrate is concentrated, transparent viscous liquid is obtained, before the as described light sensitive ceramics
Drive body；
Wherein, chloromethylmethyldichlorsilane, acrylic acid -2- hydroxyl ethyl esters, the volume ratio of triethylamine are 38.98：34.08：
50.54。
Preferably, it is first being passed through argon gas before for described Schllenk bottles, oxygen in bottle is discharged.
Preferably, in the step 1 and the step 2, reactant is reacted under the magnetic stirring speed of 500rpm.
Preferably, in the step 1 deionized water drip finish after, on Schllenk bottles installation HCl gas absorption bottles pair
The HCl gases generated in reaction process are absorbed.
Preferably, NaOH solution is housed in the HCl gases absorption bottle.
Preferably, linear polysiloxane absorbs moisture drying using excessive anhydrous magnesium sulfate in the step 1.
Preferably, reaction solution two is filtered using organic filter membrane in the step 2.
Preferably, filtrate obtains transparent viscous liquid after rotating 4h at 92 DEG C in the step 2.
Compared with the conventional method, the beneficial effects of the present invention are：
The present invention prepares the polysiloxanes ceramic forerunner of uV curable, and gained light sensitive ceramics presoma is being suitble to
Initiator be added under, when ultraviolet light 30s, can reach 80% double bond conversion rate, when 40s can to 90% double bond conversion rate,
With very efficient light-cured performance；Sample after solidification is subjected to thermogravimetic analysis (TGA), ceramic yield at 1400 DEG C can be obtained
It is 44.15%；Increasing material manufacturing is carried out using stereo lithography using polysiloxanes ceramic forerunner as raw material, pattern can be obtained
Regular cured article, smooth appearance, intensity are higher；By cured article after tubular furnace pyrolysis, the ceramics of linear contraction are obtained
Product, shrinking percentage are about 28.5%, gained ceramic product compact structure, indefectible.
Description of the drawings
Fig. 1 is the light sensitive ceramics presoma double bond conversion rate prepared of embodiment 1 with irradiation time change curve；
Fig. 2 is the 3D printing sample drawing that embodiment 1 prepares light sensitive ceramics presoma；
Fig. 3 is the 3D printing sample thermogravimetic analysis (TGA) curve graph that embodiment 2 is prepared；
Fig. 4 is the figure after the 3D printing sample pyrolysis that embodiment 2 is prepared.
Specific implementation mode
Methods of this invention will be better understood in order to enable art processes personnel, and scheme is practiced, with reference to specific
The invention will be further described for embodiment and attached drawing, but illustrated embodiment is not as a limitation of the invention.
Experimental method and detection method described in following each embodiments are unless otherwise specified conventional method；The examination
Agent and material can be commercially available on the market unless otherwise specified.
Embodiment 1
A kind of light sensitive ceramics forerunner's preparation for increases material manufacturing technology manufacture ceramic product, synthetic route is such as
Under：
In formula, n is positive integer；
Specific synthetic method is as follows：
Step 1, as shown in formula (I), the Schlenk bottles of 250mL capacity are pre-processed, ensure that gas is Ar in bottle
Gas, and anhydrous and oxygen-free, then under Ar gas shieldeds, successively by 38.98mL chloromethylmethyldichlorsilanes and 40.40mL dichloromethanes
Base vinyl silanes are added in Schllenk bottles, and are uniformly mixed under the magnetic agitation of 500rpm；10mL deionizations are taken again
Water, with the speed of 1 drop/10s be added drop-wise to it is Schllenk bottles above-mentioned in, after being added dropwise on Schllenk bottles install additional HCl gases
Absorption bottle absorbs the HCl gases generated in reaction process；It is reacted at room temperature to bubble-free and is generated, obtain reaction solution one；
Reaction solution one is placed in 45 DEG C of heating reaction 12h of oil bath, reaction finishes to obtain linear polysiloxane；
Excessive anhydrous magnesium sulfate is added into linear polysiloxane and absorbs moisture, is taken out using organic filter membrane after stirring 4h
Filter, obtains dry linear polysiloxane；3mL dimethyl vinyl chlorosilanes are added into dry linear polysiloxane to carry out
End capping reaction obtains terminated polysiloxane after end capping reaction 6h；
Step 2, the terminated polysiloxane that step 1 obtains is placed in ice bath, and is added and seals into terminated polysiloxane
Then the water removal deoxygenation THF for holding polysiloxanes isometric is charged with 34.08ml acrylic acid -2- hydroxyl ethyl esters, stirs as solvent
It mixes uniformly, the triethylamine of 50.54ml is then added dropwise thereto, rate of addition is 1 drop/5s, is reacted in ice bath after being added dropwise
4h obtains reaction solution two after completion of the reaction, and the organic filter membrane of reaction solution two is filtered, white solid is removed, and collects filtrate, then will
Filtrate rotates 4h at 92 DEG C, obtains transparent viscous liquid, as light sensitive ceramics presoma.
It should be noted that being equipped with NaOH solution in HCl gases absorption bottle.
Light-cured performance detection is carried out to the light sensitive ceramics presoma that embodiment 1 is prepared, detailed process is as follows：
The light-cured performance of the light sensitive ceramics presoma synthesized to embodiment 1 using infrared internal standard method is tested.In light
The photoinitiator of 1wt%-3wt% is added in quick ceramic forerunner, then light sensitive ceramics presoma is placed in print mold, then
Light sensitive ceramics presoma is irradiated with standing wave long ultraviolet light, be used in combination Fourier infrared spectrograph to irradiation 0s, 5s, 10s,
The sample of 15s, 20s, 25s, 30s, 35s, 40s, 50s, 60s, 80s, 100s, 120s, 180s, 240s carry out infrared test, with
Carbonyl peak is internal standard, calculates double bond conversion rate, and concrete outcome is shown in Fig. 1.
It will be seen from figure 1 that unsaturated double-bond conversion ratio is improved with the extension of irradiation time in light sensitive ceramics presoma,
Have reached nearly 80% conversion ratio in 30s, after 40s, conversion ratio has reached 90%.Before this illustrates the light sensitive ceramics that the present invention synthesizes
Driving body has very efficient ultraviolet light curable energy.
The number-average molecular weight (Mn) and weight average molecular weight (Mw) of light sensitive ceramics presoma after being cured to ultraviolet light using GPC
It is tested, test result is as follows：The number-average molecular weight Mn=2190Da of light sensitive ceramics presoma, weight average molecular weight Mw=
3940Da, the i.e. polymer are oligomer, and polymer dispersity FACTOR P DI=1.85, molecular weight distribution is wider.
Embodiment 2
Using the light sensitive ceramics presoma for being added to photoinitiator as raw material, 3D is carried out using Form2 type 3D printers and is beaten
Print operation, prints simple stereochemical structure, print result is as shown in Figure 2.
Figure it is seen that printing gained stereochemical structure surface is smooth, sharp edges are neat, internal uniform, no gas
Hole flawless has some strength.This result proves that the light sensitive ceramics presoma of the invention prepared is combinable and is light-cured at once
Type technology prepares ceramic product by the way of increasing material manufacturing, has broad application prospects.
Thermogravimetic analysis (TGA) is carried out to above-mentioned 3D printing sample and pyrolysis linear shrinkage calculates, specific experiment process is as follows：
1, thermogravimetic analysis (TGA)
Above-mentioned 3D printing sample 3-6mg is taken, using 449 F3 of STA (Netzsch Group, Germany) thermogravimetric analyzer
Thermogravimetic analysis (TGA) is carried out to sample, test condition is as follows：Temperature range：25-1400℃；Heating rate：10K/min；Mobile phase
For argon gas.Specific testing result is shown in Fig. 3.
From figure 3, it can be seen that carrying out thermogravimetic analysis (TGA) to 3D printing sample, ceramic yield is when can obtain 1400 DEG C
44.15%, ceramic yield is high, and gained ceramic dense degree is good, high mechanical strength.
2, pyrolysis linear shrinkage calculates
Above-mentioned 3D printing sample (width is about 1.4cm) is placed in tube furnace and is pyrolyzed, pyrolytical condition is as follows：Heating speed
Rate：5℃/min；400 DEG C are warming up to, keeps the temperature 120min, then be warming up to 1400 DEG C, keeps the temperature 120min, then be cooled to 500 DEG C, then
Cooled to room temperature, and logical Ar gas shieldeds in entire pyrolytic process.
Pyrolysis finishes to obtain the ceramic product of linear contraction, is specifically shown in Fig. 4, from fig. 4, it can be seen that before sintering, 3D printing
Sample Width is about 1.4cm, and width is about 1cm after sintering, after shrinking percentage 0.4/1.4=0.285, i.e. ceramic product pyrolysis
Shrinking percentage is 28.5%, and the ceramic product compact structure after pyrolysis, indefectible.
It should be noted that the present invention describes preferred embodiment, but method personnel in the art once know
Basic creative concept, then additional changes and modifications may be made to these embodiments.So appended claims are intended to explain
It is to include preferred embodiment and fall into all change and modification of the scope of the invention.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by the method personnel of this field
God and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent processes
Within be also intended to include these modifications and variations.
Claims (8)
1. a kind of light sensitive ceramics forerunner's preparation for increases material manufacturing technology manufacture ceramic product, which is characterized in that close
It is as follows at route：
In formula, n is positive integer；
Specific synthetic method is as follows：
Step 1, as shown in formula (I), under protection of argon gas, successively by chloromethylmethyldichlorsilane and dichloromethyl vinyl silicon
Alkane is added in dry Schllenk bottles, is stirred evenly, and deionized water is then added dropwise thereto, and rate of addition is 1 drop/10s,
It is reacted after being added dropwise to bubble-free and is generated at room temperature, obtain reaction solution one；Reaction solution one is placed at 45 DEG C and reacts 12h,
Reaction finishes to obtain linear polysiloxane；
It is charged with dimethyl vinyl chlorosilane after linear polysiloxane is dried and carries out end capping reaction, after end capping reaction 6h
Obtain terminated polysiloxane；
Wherein, chloromethylmethyldichlorsilane, dichloromethyl vinyl silanes, deionized water：Dimethyl vinyl chlorosilane
Volume ratio is 38.98：40.40：10：3；
Step 2, the terminated polysiloxane that step 1 obtains is placed in ice bath, and is added into terminated polysiloxane and gathers with sealing end
Then the isometric THF of siloxanes is charged with acrylic acid -2- hydroxyl ethyl esters, stirs evenly, then be added dropwise thereto as solvent
Triethylamine, rate of addition are 1 drop/5s, react 4h after being added dropwise in ice bath, obtain reaction solution two after completion of the reaction, will be anti-
It answers liquid two to filter, collects filtrate, then filtrate is concentrated, obtain transparent viscous liquid, the as described light sensitive ceramics presoma；
Wherein, chloromethylmethyldichlorsilane, acrylic acid -2- hydroxyl ethyl esters, the volume ratio of triethylamine are 38.98：34.08：
50.54。
2. the light sensitive ceramics presoma preparation side according to claim 1 for increases material manufacturing technology manufacture ceramic product
Method, which is characterized in that described Schllenk bottles is first being passed through argon gas before, and oxygen in bottle is discharged.
3. the light sensitive ceramics presoma preparation side according to claim 1 for increases material manufacturing technology manufacture ceramic product
Method, which is characterized in that in the step 1 and the step 2, reactant is reacted under the magnetic stirring speed of 500rpm.
4. the light sensitive ceramics presoma preparation side according to claim 1 for increases material manufacturing technology manufacture ceramic product
Method, which is characterized in that in the step 1 deionized water drip finish after, on Schllenk bottles installation HCl gas absorption bottles to anti-
The HCl gases that should be generated in the process are absorbed.
5. the light sensitive ceramics presoma preparation side according to claim 4 for increases material manufacturing technology manufacture ceramic product
Method, which is characterized in that NaOH solution is housed in the HCl gases absorption bottle.
6. the light sensitive ceramics presoma preparation side according to claim 1 for increases material manufacturing technology manufacture ceramic product
Method, which is characterized in that linear polysiloxane absorbs moisture drying using excessive anhydrous magnesium sulfate in the step 1.
7. the light sensitive ceramics presoma preparation side according to claim 1 for increases material manufacturing technology manufacture ceramic product
Method, which is characterized in that reaction solution two is filtered using organic filter membrane in the step 2.
8. the light sensitive ceramics presoma preparation side according to claim 1 for increases material manufacturing technology manufacture ceramic product
Method, which is characterized in that filtrate obtains transparent viscous liquid after rotating 4h at 92 DEG C in the step 2.
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| CN110028639A (en) * | 2019-04-17 | 2019-07-19 | 厦门理工学院 | A kind of photosensitivity Zr-B-Si-C ceramic forerunner and its in-situ preparation method |
| CN110028639B (en) * | 2019-04-17 | 2021-09-10 | 厦门理工学院 | Photosensitive Zr-B-Si-C ceramic precursor and in-situ preparation method thereof |
| CN110002883A (en) * | 2019-04-29 | 2019-07-12 | 西北工业大学 | A kind of polysilazane ceramic of photocuring 3D printing and preparation method thereof |
| CN110002883B (en) * | 2019-04-29 | 2021-12-14 | 西北工业大学 | Photocuring 3D printed polysilazane ceramic product and preparation method thereof |
| CN110467468A (en) * | 2019-09-19 | 2019-11-19 | 广东工业大学 | A kind of photocurable polysilazane and preparation method thereof, SiCN ceramics and preparation method thereof |
| CN114835900A (en) * | 2022-05-09 | 2022-08-02 | 西北工业大学 | Hyperbranched polyborosiloxane ceramic precursor, preparation method thereof and preparation method of Si-B-O-C ceramic |
| CN115504804A (en) * | 2022-10-18 | 2022-12-23 | 中国科学院金属研究所 | Method for manufacturing SiOC porous heat insulation structure through continuous additive manufacturing |
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