CN108344518B - A kind of preparation method of dense form PRECURSOR-DERIVED CERAMICS temperature sensor - Google Patents
A kind of preparation method of dense form PRECURSOR-DERIVED CERAMICS temperature sensor Download PDFInfo
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
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- B28B11/00—Apparatus or processes for treating or working the shaped or preshaped articles
- B28B11/24—Apparatus or processes for treating or working the shaped or preshaped articles for curing, setting or hardening
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Abstract
The present invention relates to a kind of preparation methods of dense form PRECURSOR-DERIVED CERAMICS temperature sensor, and described method includes following steps: liquid ceramic precursor being placed in liquid condition shaping mold and keeps the temperature 0.5~2h at 150 DEG C~200 DEG C, obtains molding precursor；Molding precursor is kept the temperature into 3~6h at 350 DEG C~450 DEG C, obtains precursor block；Precursor block is pyrolyzed 3~6h at 1000 DEG C~1450 DEG C, obtains PRECURSOR-DERIVED CERAMICS；Dense form PRECURSOR-DERIVED CERAMICS temperature sensor is made in the connection electrode on PRECURSOR-DERIVED CERAMICS.The method that the present invention uses liquid condition shaping, hot setting is directly carried out to liquid ceramic precursor without adding curing agent, a kind of dense form PRECURSOR-DERIVED CERAMICS temperature sensor suitable for extreme environment is made, the temperature sensor has the advantages that antioxygenic property is good, intensity is high and measurement result is accurate.
Description
Technical field
The invention belongs to temperature sensor technology field more particularly to a kind of dense form PRECURSOR-DERIVED CERAMICS temperature sensors
Preparation method.
Background technique
Applied to the temperature sensor of extreme environment, such as applied in engine or various burnings, heating system etc.
Sensor more lack, it is main challenge seek to bear extreme environment high temperature, high pressure and Strong oxdiative corrosion
Environment etc..Si sill has the micro-processing method of controllable electronic property and rapid development.But the sensor of pure Si exists
It easily degrades under high temperature, therefore is usually no more than 350 DEG C；Although the sensor of SiC base proposes Range of measuring temp
It rises, is generally also no more than 500 DEG C.
Sensor material based on PRECURSOR-DERIVED CERAMICS have excellent high-temperature stability, antioxidant anticorrosive characteristic outstanding with
And high temperature semiconductors characteristic, such as SiCN PRECURSOR-DERIVED CERAMICS, characteristic of semiconductor can achieve 1300 DEG C, it is often more important that can be with
Shaping structures are carried out using various ways.
Currently, preparation and research and development based on PRECURSOR-DERIVED CERAMICS sensor have mostly used precursor powder to be pressed,
This molding mode is unable to get complete ceramic of compact.And the device based on un-densified ceramics has the disadvantages that (1) was pyrolyzed
Easily occur shrinking non-uniform situation in journey, so as to cause the heterogeneity of institutional framework；(2) presence of hole can adsorb environment
In multiple gases, cause the variation of conductivity, so as to cause the generation of high error；(3) un-densified ceramic material itself is anti-
Oxidation susceptibility and intensity can reduce.
Currently, the mode of PRECURSOR-DERIVED CERAMICS densification mostly uses photocuring, the shortcomings which is preparation process complexity, is needed
Light curing agent is added, and cure parameter is complicated；Furthermore the introducing of light curing agent can cause the variation of conductivity, will affect sensor
The repeatability of preparation process.
Chinese patent application 201510479237.7 discloses a kind of SiAlCN polymer precursor ceramic temperature sensor
And preparation method thereof, but curing agent is added in forming method disclosed in this application, sensor preparation process may be will affect
Repeatability.
Summary of the invention
It is inadequate to solve existing PRECURSOR-DERIVED CERAMICS porosity height, compactness, so as to cause PRECURSOR-DERIVED CERAMICS obtained sensing
Device antioxygenic property and intensity is not high enough, conductivity variations unevenly have measurement error, the present invention using liquid at
The method of type directly carries out hot setting to liquid ceramic precursor under conditions of not adding curing agent, is prepared for a kind of suitable
Dense form PRECURSOR-DERIVED CERAMICS temperature sensor for extreme environment.Temperature sensor made from the method for the present invention has antioxygen
Change the advantage that performance is good, intensity is high and measurement result is accurate.
To achieve the goals above, the present invention provides a kind of preparation sides of dense form PRECURSOR-DERIVED CERAMICS temperature sensor
Method, described method includes following steps:
(1) liquid ceramic precursor is placed in liquid condition shaping mold and keeps the temperature 0.5~2h at 150 DEG C~200 DEG C, obtained
To molding precursor；
(2) the molding precursor for obtaining step (1) keeps the temperature 3~6h at 350 DEG C~450 DEG C, obtains precursor block；
(3) the precursor block for obtaining step (2) is pyrolyzed 3~6h at 1000 DEG C~1450 DEG C, obtains precursor pottery
Porcelain；
(4) dense form PRECURSOR-DERIVED CERAMICS temperature sensing is made in the connection electrode on the PRECURSOR-DERIVED CERAMICS that step (3) obtains
Device.
Particularly, the liquid ceramic precursor is polysilazane, Polycarbosilane, polysiloxanes, polyborosiloxane or poly-
Aluminium siloxanes；Preferably, the liquid ceramic precursor is polysilazane.
Preferably, the electrode is platinum electrode, gold electrode, nickel alloy electrode or graphite electrode.
Preferably, the heat preservation in step (1), the heat preservation in step (2) and/or the pyrolysis in step (3) are in indifferent gas
The lower progress of atmosphere protection, the inert atmosphere is argon atmosphere or nitrogen atmosphere.
Preferably, before liquid ceramic precursor is placed in liquid condition shaping mold, first by the liquid ceramic pioneer
Body carries out row's bubble processing.
Preferably, the row steeps processing and is carried out by the way of vacuumizing.
Preferably, the electrode is two line electrodes or four line electrodes.
Preferably, it is attached in step (4) using bonding agent；The bonding agent is graphite glue, metal paste or liquid
Ceramic precursor, the metal paste are preferably platinum slurry or tungsten slurry；The upper surface of the electrode and the PRECURSOR-DERIVED CERAMICS and/or
It is perpendicular or parallel with lower surface.
Preferably, 1 DEG C/min~5 DEG C/min heating rate is used to rise to heat preservation in step (1) and/or step (2)
Temperature；And/or the temperature of pyrolysis is risen in step (3) using 0.5 DEG C/min~1.5 DEG C/min heating rate.
Preferably, the liquid condition shaping mold is made of polytetrafluoroethylene material；And/or the liquid condition shaping mold is
Offer the liquid condition shaping mold of cyclic annular overflow launder.
The present invention at least has the following beneficial effects: compared with prior art
(1) present invention is different from the existing liquid condition shaping method for needing to be added curing agent, without adding curing agent, to liquid
State ceramic precursor directly carries out hot setting, and dense form PRECURSOR-DERIVED CERAMICS can be made；Forming method of the present invention is simple, is prepared into
This is low and will not have an impact to the conductivity of PRECURSOR-DERIVED CERAMICS, is a kind of preparation that preparation temperature sensor process is reproducible
Method.
(2) PRECURSOR-DERIVED CERAMICS uniform texture produced by the present invention and completely densification do not have to consider un-densified precursor
The porosity height of ceramics causes conductivity variations that the measurement error of temperature sensor and porosity height is caused to lead to temperature sensing
The antioxygenic property of device reduces, the influence of strength reduction etc..
(3) dense form PRECURSOR-DERIVED CERAMICS temperature sensor antioxygenic property prepared by the present invention is good, intensity is high and measurement
As a result accurate, it can be applied in the extreme environments such as high temperature, high pressure and Strong oxdiative corrosion.
(4) present invention can design different size shape mold carry out liquid molding, it can be achieved that different shape size temperature
Spend the preparation of sensor and the preparation of mini-temperature sensor.
(5) in some preferred embodiments of the present invention, using slow heating rate (0.5 DEG C/min~1.5 DEG C/
Min required pyrolysis temperature) is risen to, the precursor pottery that uniform texture, conductivity are uniform and compactness is high is advantageously formed
Porcelain.
(6) in some preferred embodiments of the present invention, the liquid condition shaping mold of use is made of polytetrafluoroethylene material,
Because polytetrafluoroethylene material is not with liquid ceramic pioneer precursor reactant and the phenomenon that be not in sticking to mould, convenient for taking out molding pioneer
Body, it is easy to operate.
Detailed description of the invention
Fig. 1 is the structural representation of the dense form PRECURSOR-DERIVED CERAMICS temperature sensor of specific embodiment preparation of the invention
Figure.
Fig. 2 is that the structure of the dense form PRECURSOR-DERIVED CERAMICS temperature sensor of another embodiment preparation of the present invention is shown
It is intended to.
Fig. 3 is that the structure of the dense form PRECURSOR-DERIVED CERAMICS temperature sensor of another specific embodiment preparation of the invention is shown
It is intended to.
The liquid condition shaping mold used in Fig. 4 one specific embodiment of the present invention.
Fig. 5 is the sectional view taken along line A-A shown in Fig. 4.
Fig. 6 is the PRECURSOR-DERIVED CERAMICS of specific embodiment preparation of the invention.
In figure: 1: PRECURSOR-DERIVED CERAMICS；2: electrode；3: graphite glue；4: die cavity；5: overflow launder；A: the precursor before being pyrolyzed
Block；B: the PRECURSOR-DERIVED CERAMICS obtained after pyrolysis.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the embodiment of the present invention, to this hair
Bright technical solution is clearly and completely described.Obviously, described embodiment is a part of the embodiments of the present invention, and
The embodiment being not all of.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work
Under the premise of every other embodiment obtained, shall fall within the protection scope of the present invention.
The present invention provides a kind of preparation methods of dense form PRECURSOR-DERIVED CERAMICS temperature sensor, and the method includes as follows
Step:
(1) liquid ceramic precursor is placed in liquid condition shaping mold and in 150 DEG C~200 DEG C (such as 150 DEG C, 160
DEG C, 170 DEG C, 180 DEG C, 190 DEG C or 200 DEG C) under keep the temperature 0.5~2h (such as 0.5,0.6,0.7,0.8,0.9,1,1.2,1.5,
1.8 or 2h), obtain molding precursor；By the liquid ceramic precursor (such as in temperature under conditions of 150 DEG C~200 DEG C
For in 150 DEG C~200 DEG C of tube furnaces) heat preservation is to be crosslinked it tentatively and curing molding.
(2) the molding precursor for obtaining step (1) is in 350 DEG C~450 DEG C (such as 350 DEG C, 360 DEG C, 370 DEG C, 380
DEG C, 390 DEG C, 400 DEG C, 410 DEG C, 420 DEG C, 430 DEG C, 440 DEG C or 450 DEG C) under keep the temperature 3~6h (such as 3,3.5,4,4.5,5,
5.5 or 6h), obtain precursor block；Will molding precursor under conditions of 350 DEG C~450 DEG C (such as temperature be 350 DEG C
~450 DEG C of tube furnace) heat preservation be in order to make form precursor realize it is fully crosslinked with solidification.
(3) the precursor block for obtaining step (2) is in 1000 DEG C~1450 DEG C (such as 1000 DEG C, 1050 DEG C, 1100
DEG C, 1150 DEG C, 1200 DEG C, 1250 DEG C, 1300 DEG C, 1350 DEG C, 1400 DEG C or 1450 DEG C) under be pyrolyzed 3~6h (such as 3,3.5,4,
4.5,5,5.5 or 6h), obtain PRECURSOR-DERIVED CERAMICS；The knot of tissue for the PRECURSOR-DERIVED CERAMICS being pyrolyzed under different pyrolysis temperatures
Structure is different, conductivity is also different.It particularly, further include to obtained elder generation before the precursor block that will be obtained is pyrolyzed
Body block is driven to polish to obtain the more regular precursor block of contour structures.
(4) dense form PRECURSOR-DERIVED CERAMICS temperature sensing is made in the connection electrode on the PRECURSOR-DERIVED CERAMICS that step (3) obtains
Device.
Liquid ceramic precursor of the present invention is polysilazane, Polycarbosilane, polysiloxanes, polyborosiloxane or poly-aluminium
Siloxanes；Preferably, the liquid ceramic precursor is polysilazane, for example, by using polysilazane as liquid ceramic pioneer
Dense form non-crystal silicon carbon nitrogen PRECURSOR-DERIVED CERAMICS temperature sensor, i.e. dense form Amorphous GaN N PRECURSOR-DERIVED CERAMICS temperature can be made in body
Sensor.It is all had using these liquid ceramic precursors as raw material PRECURSOR-DERIVED CERAMICS as made from precursor pyrolysis and hot pressing good
High-temperature temperature-resistance characteristic, unlike, due to this body structure and property of PRECURSOR-DERIVED CERAMICS, itself conductivity is different, temperature
It is different to spend sensing capability, inoxidizability is different.For example, amorphous Si CN PRECURSOR-DERIVED CERAMICS have good high high-temp stability,
High-temperature oxidation resistance and creep-resistant property.
The present invention solidifies (150 DEG C~200 DEG C of first stage solidification temperature, second stage solidification temperature using segmented high-temperature
350 DEG C~450 DEG C) compared to step high temperature solidification (such as 110 DEG C~170 DEG C of solidification temperature), it on the one hand can prevent tentatively solid
Change that temperature is excessively high so that precursor generates bubble or burns out, on the other hand the institutional framework of PRECURSOR-DERIVED CERAMICS can be made more equal
It is even, advantageously form dense form PRECURSOR-DERIVED CERAMICS.
The present invention is not particularly limited liquid condition shaping mold, and the preferably described liquid condition shaping mold uses polytetrafluoro
Vinyl material is made, and the material is not with ceramic setter precursor reactant and the phenomenon that be not in sticking to mould, convenient for molding precursor demoulding；
Preferably, the liquid condition shaping mold is the liquid condition shaping mold for offering cyclic annular overflow launder, as shown in figure 4, the die cavity 4
Outside offer cyclic annular overflow launder 5, for guaranteeing that ceramic precursor will not largely be hoarded around die cavity 4, convenient for molding
The demoulding of precursor.The precursor that the structure of the die cavity of the liquid condition shaping mold can need to use according to real sensor is made pottery
The structure of porcelain is designed accordingly, such as die cavity can be using the abnormity design such as H-shaped, rodlike or bone-shaped.The die cavity
Quantity can carry out any amount of design according to actual needs, such as can be 4,6,8 or 10.
According to some preferred embodiments, the electrode be platinum electrode, gold electrode, nickel alloy electrode or graphite electrode,
Such as select platinum line, gold thread, nickeline wire or graphite flake that platinum electrode, gold electrode, nickel alloy electrode or graphite electrode is respectively prepared；
The electrode is two line electrodes or four line electrodes.For example, the PRECURSOR-DERIVED CERAMICS low for conductivity, using two-wire system design or three
Line sets up meter；The PRECURSOR-DERIVED CERAMICS high for conductivity, is designed using four-wire system, can be measured and be missed to avoid electrode polarization bring
Difference.
According to some preferred embodiments, it is attached in step (4) using bonding agent；The bonding agent is graphite
Glue, metal paste or liquid ceramic precursor；The metal paste is that platinum is starched or tungsten is starched；For example, as the dense form pioneer of preparation
It, can be using graphite glue as bonding agent when body ceramic temperature sensor is applied to non-oxidizing atmosphere.The electrode and the elder generation
The upper and lower surfaces for driving body ceramics are perpendicular or parallel.As shown in Figure 1, being designed using two-wire system, two electrodes 1 pass through graphite
Glue 3 is connected in parallel at the upper and lower surfaces of PRECURSOR-DERIVED CERAMICS 2 respectively, and the electrode 1 is made pottery with the precursor in position
The upper and lower surfaces of porcelain 2 are parallel.As shown in Fig. 2, being designed using two-wire system, at the substantially intermediate position of PRECURSOR-DERIVED CERAMICS 2
Aperture is then placed in electrode 1, then is attached using liquid ceramic precursor as bonding agent, so that the electrode 1 is in position
It is upper vertical with the upper and lower surfaces of the PRECURSOR-DERIVED CERAMICS 2.As shown in figure 3, being designed using four-wire system, the precursor pottery
Porcelain 2 is H-shaped, in the substantially intermediate position aperture of the upper and lower surfaces of H-shaped PRECURSOR-DERIVED CERAMICS 2, is respectively put into two electrodes 1,
Be attached using bonding agent, may be implemented four line electrode measuring resistances, the electrode 1 in position with the PRECURSOR-DERIVED CERAMICS 2
Upper and lower surfaces it is vertical.
According to some preferred embodiments, in the heat preservation in step (1), the heat preservation in step (2) and/or step (3)
Pyrolysis be to be carried out under inert atmosphere protection, the inert atmosphere be argon atmosphere or nitrogen atmosphere.
According to some preferred embodiments, before liquid ceramic precursor is placed in liquid condition shaping mold, first will
The liquid ceramic precursor carries out row's bubble processing；The row steeps processing and is carried out by the way of vacuumizing.Such as especially pair
Vacuum method is needed to exclude the bubble in liquid ceramic precursor in the biggish liquid ceramic precursor of viscosity.
In the present invention to liquid ceramic precursor carry out row bubble processing, be conducive to improve PRECURSOR-DERIVED CERAMICS ceramic yield with
And compactness.Tentatively crosslinking and solidification, fully crosslinked and solidification and pyrolysis are in order to anti-in an inert atmosphere in the present invention
Only the brittleness of PRECURSOR-DERIVED CERAMICS is excessive, conducive to the high PRECURSOR-DERIVED CERAMICS of good forming effect, compactness is obtained.
According in some preferred embodiment steps (1) and/or step (2) using 1 DEG C/min~5 DEG C/min (such as
1,2,3,4 or 5 DEG C/min) heating rate rise to the temperature of heat preservation；And/or 0.5 DEG C/min~1.5 DEG C of the middle use of step (3)/
Min (such as 0.5,0.6,0.7,0.8,0.9,
1,1.1,1.2,1.3,1.4 or 1.5 DEG C/min) heating rate rise to the temperature of pyrolysis.Guarantor is risen in the present invention
The heating rate that the heating rate of temperature especially rises to 1000 DEG C~1450 DEG C of pyrolysis temperature can not be excessive, excessive heating
Rate is unfavorable for forming the PRECURSOR-DERIVED CERAMICS of uniform texture, and is unfavorable for the densification of PRECURSOR-DERIVED CERAMICS.
The method that the present invention uses liquid condition shaping, does not add curing agent, directly progress hot setting, and used when heat preservation
Heating rate is relatively slow (1 DEG C/min~5 DEG C/min), in pyrolysis step using slow heating rate (0.5 DEG C/min~1.5 DEG C/
Min), these common factors make the present invention that dense form PRECURSOR-DERIVED CERAMICS temperature sensor be made.
Embodiment 1
Using liquid condition shaping mold as shown in Figure 4 (the liquid condition shaping mold is made of polytetrafluoroethylene material), system
A kind of standby dense form PRECURSOR-DERIVED CERAMICS temperature sensor, the PRECURSOR-DERIVED CERAMICS are SiCN PRECURSOR-DERIVED CERAMICS, and the electrode is platinum
Electrode, the electrode are connected on the SiCN PRECURSOR-DERIVED CERAMICS using liquid polysilazane as bonding agent.The SiCN is first
Body ceramics are driven to be prepared as follows.
Firstly, (vacuumizing 1h) excludes the bubble in liquid polysilazane in the way of vacuumizing, then by it by liquid
The polysilazane of state pours into liquid condition shaping mold；Then, it is passed through argon atmosphere, in tube furnace, with the liter of 3 DEG C/min
Warm rate is raised to 180 DEG C, and keeps the temperature 1h and be tentatively crosslinked and curing molding, obtains molding precursor；Then pioneer will be formed
Body takes out from liquid condition shaping mold, and molding precursor is put into tube furnace, with the liter of 3 DEG C/min under argon atmosphere protection
Warm rate is raised to 350 DEG C, and keeps the temperature 4h and carry out the fully crosslinked of precursor and solidification, obtains fully crosslinked precursor block；
Finally, carrying out high temperature pyrolysis after precursor block is polished under 1000 DEG C (pyrolysis temperature), entire pyrolytic process is in argon
It being carried out under gas atmosphere protection, heating rate is 1 DEG C/min, it is cooling with furnace temperature after heat preservation 3h (pyrolysis time), it obtains block-like
SiCN PRECURSOR-DERIVED CERAMICS.
The porosity of SiCN PRECURSOR-DERIVED CERAMICS manufactured in the present embodiment is 0%, density 2.08g/cm3, by 1000 DEG C
Oxidation weight gain obtained by lower oxidation 40min is 1.56wt%, shrinking percentage 24%.It illustrates, the hole in the present embodiment
Rate is obtained by standard drainage measurement；The shrinking percentage of PRECURSOR-DERIVED CERAMICS refers to the pioneer before pyrolysis in the present embodiment
The difference of the size of the PRECURSOR-DERIVED CERAMICS obtained after the size and pyrolysis of body block accounts for the size of the precursor block before pyrolysis
Percentage.
Embodiment 2
Embodiment 2 is substantially the same manner as Example 1, the difference is that: pyrolysis temperature is 1100 DEG C.
Embodiment 3
Embodiment 3 is substantially the same manner as Example 1, the difference is that: pyrolysis temperature is 1200 DEG C.
Embodiment 4
Embodiment 4 is substantially the same manner as Example 1, the difference is that: pyrolysis temperature is 1300 DEG C.
Embodiment 5
Embodiment 5 is substantially the same manner as Example 1, the difference is that: pyrolysis time 6h.
Embodiment 6
Embodiment 6 is substantially the same manner as Example 1, the difference is that: heating rate in pyrolytic process is 1.5 DEG C/
min。
Embodiment 7
Embodiment 7 is substantially the same manner as Example 1, the difference is that: the heating rate in pyrolytic process is 2 DEG C/min.
SiCN PRECURSOR-DERIVED CERAMICS manufactured in the present embodiment surface occurs compared with crackle.
Embodiment 8
Embodiment 8 is substantially the same manner as Example 1, the difference is that: the heating rate in pyrolytic process is 5 DEG C/min.
There is larger crackle in SiCN PRECURSOR-DERIVED CERAMICS manufactured in the present embodiment surface.
Embodiment 9
Embodiment 9 is substantially the same manner as Example 1, the difference is that: the heating rate in pyrolytic process is 10 DEG C/min.
SiCN PRECURSOR-DERIVED CERAMICS manufactured in the present embodiment is broken, can not form.
Embodiment 10
Embodiment 10 is substantially the same manner as Example 1, the difference is that: it is passed through argon atmosphere, in tube furnace, with
The heating rate of 3 DEG C/min is raised to 150 DEG C, and keeps the temperature 1h and be tentatively crosslinked and curing molding, obtains molding precursor.
Embodiment 11
Embodiment 11 is substantially the same manner as Example 1, the difference is that: by the identical step of embodiment 1 (including liquid
The dosage of state polysilazane) block-like SiCN PRECURSOR-DERIVED CERAMICS is prepared, three repeated experiments are carried out, three parts of block-like SiCN are obtained
PRECURSOR-DERIVED CERAMICS, conductivity are respectively 4.8 × 10-11S/m、4.7×10-11S/m and 4.8 × 10-11S/m.Three parts block-like
The average oxidation weight gain of SiCN PRECURSOR-DERIVED CERAMICS, averag density, mean porosities and average shrinkage ratio are as shown in table 1.
Comparative example 1
Comparative example 1 obtains polysilazane cured product by identical high temperature curing conditions in embodiment 1, and polysilazane is consolidated
Change product successively crushed, grind and sieve after obtain powdered precursor, pressing pressure be 400MPa under the conditions of into
Row powder pressing forming, dwell time 6min obtain blocky precursor；1000 after finally blocky precursor is polished
High temperature pyrolysis is carried out under DEG C (pyrolysis temperature), entire pyrolytic process carries out under argon atmosphere protection, and heating rate is 1 DEG C/
Min is pyrolyzed after 3h with furnace temperature cooling, obtains block-like SiCN PRECURSOR-DERIVED CERAMICS.
Comparative example 2
Comparative example 2 is substantially the same manner as Example 1, the difference is that: it is passed through argon atmosphere, in tube furnace, with 3
DEG C/heating rate of min is raised to 110 DEG C, and keep the temperature 1h and be tentatively crosslinked and curing molding, obtain molding precursor.
Comparative example 3
A kind of SiCN PRECURSOR-DERIVED CERAMICS temperature sensor is prepared, including probe and lead, lead are connected on probe, lead
For platinum line, the probe is made of the raw material of following portions by weight: 5 parts and 95 parts of liquid polysilazane of cumyl peroxide.
The preparation method of the SiCN PRECURSOR-DERIVED CERAMICS temperature sensor, comprising the following steps:
(a) cumyl peroxide will be contained and liquid polysilazane is placed in reaction kettle, stirred 2.0 hours at 90 DEG C,
Mixing speed is 900 revs/min, is cooled to room temperature and vacuumizes 1.0 hours to temperature；(b) mixed liquor obtained by step (a) is poured into
Solidify 20min in mold under 350nm ultraviolet light and obtains probe biscuit；(c) biscuit is popped one's head under nitrogen protection, in 1000
It is pyrolyzed 4 hours and is popped one's head at DEG C；(d) in upper connecting lead wire of popping one's head in up to SiCN PRECURSOR-DERIVED CERAMICS temperature sensor.
Comparative example 4
Comparative example 4 and comparative example 3 are essentially identical, the difference is that: mixed liquor obtained by step (a) is poured into mold by (b)
In solidify at 170 DEG C obtain within 1 hour probe biscuit.
Comparative example 5
Comparative example 5 is substantially the same manner as Example 11, the difference is that: it is added by the 6wt% of liquid polysilazane dosage
Cumyl peroxide obtains the mixed liquor of the two, and the mixed liquor is stirred 2.0 hours, and mixing speed is 900 revs/min
Clock, is cooled to room temperature to vacuumize 1.0 hours to temperature and is placed in liquid condition shaping mold.
Comparative example 5 obtains three parts of block-like SiCN PRECURSOR-DERIVED CERAMICSs, and conductivity is respectively 4.6 × 10-6S/m、9.6×
10-8S/m and 3.6 × 10-9S/m。
Table 1: the performance of dense form PRECURSOR-DERIVED CERAMICS prepared by Examples 1 to 6, embodiment 10~11 and comparative example 1~4
Index.
Symbol-expression does not test the preparation of corresponding performance.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (11)
1. a kind of preparation method of dense form PRECURSOR-DERIVED CERAMICS temperature sensor, which is characterized in that the method includes walking as follows
It is rapid:
(1) liquid ceramic precursor is placed in liquid condition shaping mold and keeps the temperature 0.5~2h at 150 DEG C~200 DEG C, obtained into
Type precursor；
(2) the molding precursor for obtaining step (1) keeps the temperature 3~6h at 350 DEG C~450 DEG C, obtains precursor block；
(3) the precursor block for obtaining step (2) is pyrolyzed 3~6h at 1000 DEG C~1450 DEG C, obtains PRECURSOR-DERIVED CERAMICS；
(4) dense form PRECURSOR-DERIVED CERAMICS temperature sensor is made in the connection electrode on the PRECURSOR-DERIVED CERAMICS that step (3) obtains.
2. preparation method according to claim 1, it is characterised in that:
The liquid ceramic precursor is polysilazane, Polycarbosilane, polysiloxanes, polyborosiloxane or polyaluminosiloxane.
3. preparation method according to claim 1, it is characterised in that:
The electrode is platinum electrode, gold electrode, nickel alloy electrode or graphite electrode.
4. preparation method according to any one of claims 1 to 3, it is characterised in that:
Heat preservation in step (1), the heat preservation in step (2) and/or the pyrolysis in step (3) are carried out under inert atmosphere protection
, the inert atmosphere is argon atmosphere or nitrogen atmosphere.
5. preparation method according to any one of claims 1 to 3, it is characterised in that:
Before liquid ceramic precursor is placed in liquid condition shaping mold, first the liquid ceramic precursor is carried out at row's bubble
Reason.
6. preparation method according to claim 5, it is characterised in that:
The row steeps processing and is carried out by the way of vacuumizing.
7. preparation method according to any one of claims 1 to 3, it is characterised in that:
The electrode is two line electrodes or four line electrodes.
8. preparation method according to any one of claims 1 to 3, it is characterised in that:
It is attached in step (4) using bonding agent；
The bonding agent is graphite glue, metal paste or liquid ceramic precursor；And/or
The upper and lower surfaces of the electrode and the PRECURSOR-DERIVED CERAMICS are perpendicular or parallel.
9. preparation method according to claim 8, it is characterised in that:
The metal paste is that platinum is starched or tungsten is starched.
10. preparation method according to any one of claims 1 to 3, it is characterised in that:
The temperature of heat preservation is risen in step (1) and/or step (2) using 1 DEG C/min~5 DEG C/min heating rate；And/or
The temperature of pyrolysis is risen in step (3) using 0.5 DEG C/min~1.5 DEG C/min heating rate.
11. preparation method according to any one of claims 1 to 3, it is characterised in that:
The liquid condition shaping mold is made of polytetrafluoroethylene material；And/or
The liquid condition shaping mold is the liquid condition shaping mold for offering cyclic annular overflow launder.
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