CN103101258A - SiOC/C laminated composite ceramic and preparation method thereof - Google Patents
SiOC/C laminated composite ceramic and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a SiOC/C laminated composite ceramic and preparation method thereof. The preparation method comprises the following steps: by using 25-38% by weight of hydrogen-containing silicone oil, 29-41% by weight of ethanediamine and 30-40% by weight of paper as raw materials, repeatedly dipping laminated paper in Si-O-N-C organic polymer formed through the reaction of hydrogen-containing silicone oil and ethanediamine to obtain Si-O-N-C/paper laminated composite prefabrication; sintering the laminated composite prefabrication to obtain compact SiOC/C laminated composite ceramic. The preparation method provided by the invention is simple, easy to operate, high in ceramic yield, and the obtained ceramic material has good heat stability. The SiOC/C laminated composite ceramic prepared by the invention can be widely applied to high-temperature material field such as machinery, aviation, energy sources and military.
Description
Technical field
The present invention relates to a kind of layered composite ceramic material and preparation method thereof, be specifically related to a kind ofly prepare SiOC/C layered composite ceramic and preparation method thereof with containing hydrogen silicone oil and paper.
Background technology
In machinery, Aero-Space, the energy and the high-temperature material such as military field, the requirement at aspects such as specific strength, specific stiffness, hardness, toughness, anti-wear performance, decay resistance and high-temperature behaviors grows with each passing day to material.Ceramic material is as a kind of material of function admirable, and is low due to toughness, fragility is large, survivability is poor, has limited its application in a lot of fields, and the ceramist is attempting to improve its toughness by the whole bag of tricks always for these years.A focus of current ceramic material Research on Toughening is the ceramic base laminar composite, and the overall structure that it becomes pottery is layer structure, copies the occurring in nature shell to utilize the meticulous compound performance that reaches excellence of simple component.This design is to be based upon on the basis of energy dissipation, it is developed into a kind of to the insensitive material of defective.
Preparation composite ceramics raw material used is mostly chemical industry and raw mineral materials at present, and these pit woods are just day by day exhausted, needs to seek renewable resource and prepares layered composite ceramic.Disclose a kind of novel hydroxyapatite/SiOC biological ceramic composite material and preparation method thereof in Chinese patent CN 200910072193.0, disclose SiAlONC pottery with containing hydrogen silicone oil and the preparation of Al powder and preparation method thereof in the applicant's Chinese patent CN200410044158.5.And have no report about preparing SiOC/C layered composite ceramic and preparation method thereof with paper and containing hydrogen silicone oil.
Summary of the invention
It is low that technical problem to be solved by this invention is to provide a kind of production cost, and the preparation method is simple, easily operation, SiOC/C layered composite ceramic that production efficiency is high and preparation method thereof.
The technical scheme that the present invention solves the problems of the technologies described above employing is: a kind of SiOC/C layered composite ceramic, it is characterized in that: it is take paper, containing hydrogen silicone oil, ethylenediamine as raw material, in raw material, each weight percentages of components is: containing hydrogen silicone oil 25 ~ 38%, ethylenediamine 29% ~ 41%, paper 30 ~ 40%, stack of papers is flooded in the Si-O-N-C organic polymer of containing hydrogen silicone oil and reacting ethylenediamine formation repeatedly, obtains the compound precast body of Si-O-N-C/ paper stratiform; The compound precast body of stratiform obtains fine and close SiOC/C layered composite ceramic through sintering.
Take amorphous state as main, density is 2.0 ~ 2.1g/cm to the layered composite ceramic that the present invention obtains between 1200 ~ 1750 ℃
3, bending strength is 100 ~ 330Mpa, fracture toughness is 2.09 ~ 2.11MPam
1/2, Vickers hardness is 0.5 ~ 6.4Gpa, the output capacity of pottery reaches 87 ~ 90%.
Paper of the present invention is the various paper such as newspaper, filter paper, rice paper and account book paper.Described stack of papers is the 100-400 layer.
The preparation method of the above-mentioned SiOC/C layered composite ceramic of the present invention, it comprises the following steps: a, 1:1 ~ 2:3 gets containing hydrogen silicone oil and ethylenediamine mixes by weight percentage, be constantly to stir 2 ~ 24 hours under the condition of 0 ~ 100 ℃ in temperature, reaction forms the Si-O-N-C organic polymer; B, get Si-O-N-C organic polymer 60 ~ 70% by weight percentage, paper 30 ~ 40%, repeatedly flood, concrete grammar is that the paper of 100 ~ 400 layers was flooded 10-30 minute in the Si-O-N-C organic polymer, taking-up is dried under temperature 80-120 ℃, dipping repeatedly, obtains the compound precast body of Si-O-N-C/ paper stratiform so repeatedly; C, the compound precast body of stratiform is contained in hot pressing or gas pressure sintering stove, vacuumize in burner hearth, begin to be heated to 1200 ℃, then pass into nitrogen, and remain 1 atmospheric nitrogen, and be warming up to 1400 ℃ of insulations 1 hour, then continue to be warming up between 1600 ~ 1750 ℃, be incubated 1 ~ 2 hour, obtain fine and close SiOC/C layered composite ceramic after sintering.
The present invention by flooding hydrogeneous organic silicone oil precursor transformation approach, through technical process such as cracking hot pressing, is prepared into the SiOC/C layered composite ceramic with stack of papers.On the one hand, this class renewable resource of newspaper is fully utilized, reach ecology.On the other hand, also provide good approach for the deep processing of timber.Simultaneously, utilize the fibre composition of paper, can also obtain the many excellent properties of woodceramics, as performances such as good thermal insulation, wear-resistant, corrosion-resistant, damping, electricity and electromagnetic shieldings, and the performance such as high-ratio surface, lightweight, porous, have very large application potential at industrial circle.
The present invention adopts cheap organic containing hydrogen silicone oil as the primary raw material of preceramic organosilicon polymer body, with paper as the lamination component, from reducing the cost of preceramic organosilicon polymer body.Preparation method of the present invention is simple, easily operation, and ceramic output capacity is high, and the thermal stability of the ceramic material that obtains is good.The SiOC/C layered composite ceramic material of the present invention preparation can be widely used in machinery, Aero-Space, the energy and the high-temperature material such as military field.
The specific embodiment
The present invention will be further described below in conjunction with embodiment.
A kind of SiOC/C layered composite ceramic of the present invention, it is take paper, containing hydrogen silicone oil, ethylenediamine as raw material, in raw material, each weight percentages of components is: containing hydrogen silicone oil 25 ~ 38%, ethylenediamine 29% ~ 41%, paper 30 ~ 40%, stack of papers is flooded in the Si-O-N-C organic polymer of containing hydrogen silicone oil and reacting ethylenediamine formation repeatedly, obtains the compound precast body of Si-O-N-C/ paper stratiform; The compound precast body of stratiform obtains fine and close SiOC/C layered composite ceramic through sintering.Take amorphous state as main, density is 2.0 ~ 2.1g/cm to the layered composite ceramic that the present invention obtains between 1200 ~ 1750 ℃
3, bending strength is 100 ~ 330Mpa, fracture toughness is 2.09 ~ 2.11MPam
1/2, Vickers hardness is 0.5 ~ 6.4Gpa, the output capacity of pottery reaches 87 ~ 90%.
Paper of the present invention is the various paper such as newspaper, filter paper, rice paper and account book paper.Described stack of papers is the 100-400 layer.
Embodiment 1: a kind of preparation method of SiOC/C layered composite ceramic, it comprises the following steps: a, 1:1 ~ 2:3 gets containing hydrogen silicone oil and ethylenediamine mixes by weight percentage, be constantly to stir 2 ~ 24 hours under the condition of 0 ~ 100 ℃ in temperature, reaction forms the Si-O-N-C organic polymer; B, get Si-O-N-C organic polymer 60 ~ 70% by weight percentage, paper 30 ~ 40%, repeatedly flood, concrete grammar is that the paper of 100 ~ 400 layers was flooded 10-30 minute in the Si-O-N-C organic polymer, taking-up is dried under temperature 80-120 ℃, dipping repeatedly, obtains the compound precast body of Si-O-N-C/ paper stratiform so repeatedly; C, the compound precast body of stratiform is contained in hot pressing or gas pressure sintering stove, vacuumize in burner hearth, begin to be heated to 1200 ℃, then pass into nitrogen, and remain 1 atmospheric nitrogen, and be warming up to 1400 ℃ of insulations 1 hour, then continue to be warming up between 1600 ~ 1750 ℃, be incubated 1 ~ 2 hour, obtain fine and close SiOC/C layered composite ceramic after sintering.
The pottery output capacity is 88%, and density is 2.1g/cm
3, bending strength is 329MPa, fracture toughness is 2.1MPam
1/2, Vickers hardness is 6.4Gpa.
The present invention adopts cheap organic containing hydrogen silicone oil as the primary raw material of preceramic organosilicon polymer body, with paper as the lamination component, from reducing the cost of preceramic organosilicon polymer body.Preparation method of the present invention is simple, easily operation, and ceramic output capacity is high, and the thermal stability of the ceramic material that obtains is good.The SiOC/C layered composite ceramic material of the present invention preparation can be widely used in machinery, Aero-Space, the energy and the high-temperature material such as military field.
Embodiment 2: the difference of the present embodiment and embodiment 1 is; it also increases b ˊ step between b, c step: it is that the compound precast body of Si-O-N-C/ paper stratiform is contained in tubular type atmosphere protection stove; be to pass into the nitrogen that flow is 200 ~ 500ml/min between 20 ~ 1200 ℃ in temperature; programming rate is controlled at 0.1 ~ 10 ℃/min; reacted 6 ~ 10 hours; the compound precast body of Si-O-N-C/ paper stratiform is carried out cracking, obtain the compound precast body of Si-O-N-C/ paper stratiform after cracking.
Embodiment 3: a kind of preparation method of SiOC/C layered composite ceramic, it comprises the following steps: a, containing hydrogen silicone oil 169ml, ethylenediamine 270ml are mixed, use oxolane 500ml and n-hexane 250ml as solvent, constantly stirred at normal temperatures 8 ~ 12 hours, reaction forms the Si-O-N-C organic polymer; B, get Si-O-N-C organic polymer 440g by weight percentage, paper 207g floods repeatedly, concrete grammar is that the newspaper that 320 layers of weight are 207g was flooded 30 minutes in the Si-O-N-C organic polymer, taking-up is oven dry at 100 ℃ of temperature, dipping repeatedly, obtains the compound precast body of Si-O-N-C/ paper stratiform so repeatedly; B ˊ, the compound precast body of Si-O-N-C/ paper stratiform is contained in tubular type atmosphere protection stove, be to pass into the nitrogen that flow is 500ml/min between 20 ~ 1200 ℃ in temperature, programming rate is controlled at 5 ℃/min, insulation is 1 hour when temperature reaches 1200 ℃, the compound precast body of Si-O-N-C/ paper stratiform is carried out cracking, obtain the compound precast body of Si-O-N-C/ paper stratiform after cracking; C, the compound precast body of stratiform is contained in hot pressing or gas pressure sintering stove, vacuumize in burner hearth, begin heating, programming rate is controlled at 5 ℃/min, passes into nitrogen after being heated to 1200 ℃, and remains 1 atmospheric nitrogen, then be warming up to 1400 ℃ of insulations 1 hour with 5 ℃/min of programming rate, then continue to be warming up between 1700 ℃ with 5 ℃/min of programming rate, be incubated 1 hour, obtain fine and close SiOC/C layered composite ceramic after sintering.
The pottery output capacity is 88%, and density is 2.1g/cm
3, bending strength is 329MPa, fracture toughness is 2.1MPam
1/2, Vickers hardness is 6.4Gpa.
Embodiment 4: a kind of preparation method of SiOC/C layered composite ceramic, it comprises the following steps: a, containing hydrogen silicone oil 198ml, ethylenediamine 200ml are mixed, use oxolane 500ml and n-hexane 250ml as solvent, constantly stirred at normal temperatures 8 ~ 12 hours, reaction forms the Si-O-N-C organic polymer; B, get Si-O-N-C organic polymer 400g by weight percentage, paper 200g floods repeatedly, concrete grammar is that the newspaper that 320 layers of weight are 200g was flooded 20 minutes in the Si-O-N-C organic polymer, taking-up is oven dry at 110 ℃ of temperature, dipping repeatedly, obtains the compound precast body of Si-O-N-C/ paper stratiform so repeatedly; C, the compound precast body of stratiform is contained in hot pressing or gas pressure sintering stove, vacuumize in burner hearth, begin heating, programming rate is controlled at 5 ℃/min, passes into nitrogen after being heated to 1200 ℃, and remains 1 atmospheric nitrogen, then be warming up to 1400 ℃ of insulations 1 hour with 5 ℃/min of programming rate, then continue to be warming up between 1750 ℃ with 5 ℃/min of programming rate, be incubated 1 hour, obtain fine and close SiOC/C layered composite ceramic after sintering.
The pottery output capacity is 87%, and density is 2.05g/cm
3, bending strength is 255MPa, fracture toughness is 2.11MPam
1/2, Vickers hardness is 3.4Gpa.
Embodiment 5: a kind of preparation method of SiOC/C layered composite ceramic, it comprises the following steps: a, containing hydrogen silicone oil 169ml, ethylenediamine 200ml are mixed, use oxolane 500ml and n-hexane 250ml as solvent, constantly stirred at normal temperatures 8 ~ 12 hours, reaction forms the Si-O-N-C organic polymer; B, get Si-O-N-C organic polymer 360g by weight percentage, paper 180g floods repeatedly, concrete grammar is that the newspaper that 300 layers of weight are 180g was flooded 30 minutes in the Si-O-N-C organic polymer, taking-up is oven dry at 120 ℃ of temperature, dipping repeatedly, obtains the compound precast body of Si-O-N-C/ paper stratiform so repeatedly; B ˊ, the compound precast body of Si-O-N-C/ paper stratiform is contained in tubular type atmosphere protection stove, be to pass into the nitrogen that flow is 500ml/min between 20 ~ 1000 ℃ in temperature, programming rate is controlled at 5 ℃/min, insulation is 1 hour when temperature reaches 1000 ℃, the compound precast body of Si-O-N-C/ paper stratiform is carried out cracking, obtain the compound precast body of Si-O-N-C/ paper stratiform after cracking; C, the compound precast body of stratiform is contained in hot pressing or gas pressure sintering stove, vacuumize in burner hearth, begin heating, programming rate is controlled at 5 ℃/min, passes into nitrogen after being heated to 1200 ℃, and remains 1 atmospheric nitrogen, then be warming up to 1400 ℃ of insulations 1 hour with 5 ℃/min of programming rate, then continue to be warming up between 1650 ℃ with 5 ℃/min of programming rate, be incubated 1 hour, obtain fine and close SiOC/C layered composite ceramic after sintering.
The pottery output capacity is 87%, and density is 2.0g/cm
3, bending strength is 245MPa, fracture toughness is 2.1MPam
1/2, Vickers hardness is 2.4Gpa.
Claims (5)
1. SiOC/C layered composite ceramic, it is characterized in that: it is take paper, containing hydrogen silicone oil, ethylenediamine as raw material, in raw material, each weight percentages of components is: containing hydrogen silicone oil 25 ~ 38%, ethylenediamine 29% ~ 41%, paper 30 ~ 40%, stack of papers is flooded in the Si-O-N-C organic polymer of containing hydrogen silicone oil and reacting ethylenediamine formation repeatedly, obtains the compound precast body of Si-O-N-C/ paper stratiform; The compound precast body of stratiform obtains fine and close SiOC/C layered composite ceramic through sintering.
2. SiOC/C layered composite ceramic according to claim 1, it is characterized in that: described paper is newspaper or filter paper or rice paper or account book paper.
3. SiOC/C layered composite ceramic according to claim 1, it is characterized in that: described stack of papers is the 100-400 layer.
4. the preparation method of the described SiOC/C layered composite ceramic of claim 1, it is characterized in that: it comprises the following steps: a, 1:1 ~ 2:3 gets containing hydrogen silicone oil and ethylenediamine mixes by weight percentage, be constantly to stir 2 ~ 24 hours under the condition of 0 ~ 100 ℃ in temperature, reaction forms the Si-O-N-C organic polymer; B, get Si-O-N-C organic polymer 60 ~ 70% by weight percentage, paper 30 ~ 40%, repeatedly flood, concrete grammar is that the paper of 100 ~ 400 layers was flooded 10-30 minute in the Si-O-N-C organic polymer, taking-up is dried under temperature 80-120 ℃, dipping repeatedly, obtains the compound precast body of Si-O-N-C/ paper stratiform so repeatedly; C, the compound precast body of stratiform is contained in hot pressing or gas pressure sintering stove, vacuumize in burner hearth, begin to be heated to 1200 ℃, then pass into nitrogen, and remain 1 atmospheric nitrogen, and be warming up to 1400 ℃ of insulations 1 hour, then continue to be warming up between 1600 ~ 1750 ℃, be incubated 1 ~ 2 hour, obtain fine and close SiOC/C layered composite ceramic after sintering.
5. the preparation method of SiOC/C layered composite ceramic according to claim 4; it is characterized in that: also comprise b ˊ step between b, c step: it is that the compound precast body of Si-O-N-C/ paper stratiform is contained in tubular type atmosphere protection stove; be to pass into the nitrogen that flow is 200 ~ 500ml/min between 20 ~ 1200 ℃ in temperature; programming rate is controlled at 0.1 ~ 10 ℃/min; reacted 6 ~ 10 hours; the compound precast body of Si-O-N-C/ paper stratiform is carried out cracking, obtain the compound precast body of Si-O-N-C/ paper stratiform after cracking.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105734956A (en) * | 2016-01-29 | 2016-07-06 | 天津大学 | Method for preparing silicon dioxide/silicon, oxygen and carbon composition coating on surface of carbon material |
| CN106631080A (en) * | 2017-01-25 | 2017-05-10 | 厦门大学 | Manufacturing method of Si-O-C ceramic flexible substrate |
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| CN100999412A (en) * | 2006-12-14 | 2007-07-18 | 哈尔滨工业大学（威海） | Sialon quasi monodimension nanometer material and its preparation method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105734956A (en) * | 2016-01-29 | 2016-07-06 | 天津大学 | Method for preparing silicon dioxide/silicon, oxygen and carbon composition coating on surface of carbon material |
| CN106631080A (en) * | 2017-01-25 | 2017-05-10 | 厦门大学 | Manufacturing method of Si-O-C ceramic flexible substrate |
| CN106631080B (en) * | 2017-01-25 | 2019-04-16 | 厦门大学 | A kind of preparation method of Si-O-C ceramics flexible base board |
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Application publication date: 20130515 |