CN100372809C - Process for preparation of carbon/carbon-silicon carbide composites by liquid-gas phase pyrolysis of matrix precursor - Google Patents
Process for preparation of carbon/carbon-silicon carbide composites by liquid-gas phase pyrolysis of matrix precursor Download PDFInfo
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- CN100372809C CN100372809C CNB2006100430344A CN200610043034A CN100372809C CN 100372809 C CN100372809 C CN 100372809C CN B2006100430344 A CNB2006100430344 A CN B2006100430344A CN 200610043034 A CN200610043034 A CN 200610043034A CN 100372809 C CN100372809 C CN 100372809C
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Abstract
The present invention discloses a method for preparing carbon /carbon-silicon carbide composite materials, which comprises the following steps: a prepared reinforcement body is arranged in a baking oven to be baked; graphite cushion blocks are arranged at the upper end and the lower end of the prepared reinforcement body, and are arranged on copper electrodes after the graphite cushion blocks are tightly fixed; hexamethyl-disilazane precursors are injected in a settling chamber, and nitrogen gas is continuously led into the settling chamber for removing air deposited in the settling chamber; a power supply is switched on to heat the prepared reinforcement body, the chamber temperature is evenly increased to 700 to 900 DEG C within 10 minutes, and hexamethyl-disilazane precursors are continuously injected in the settling chamber for keeping the height of a liquid surface; after heat preservation for 0.5 to 15 hours, the power supply is switched off, and the temperature is naturally reduced to the chamber temperature; the residual hexamethyl-disilazane precursors in the settling chamber are recovered, and the product is extracted. Because the present invention adopts the hexamethyl-disilazane as the base precursors, and the prepared reinforcement body is directly switched on and heated, the preparing time is reduced to 0.5 to 15 hours than that of the prior art, which is more than one month; the preparation can be completed after one-time continuous sedimentary cycle; the use ratio of the precursors is increased to 50% from that of the prior art, which is less than 5%.
Description
Technical field
The present invention relates to a kind of method for preparing carbon/carbon fiber reinforced silicon carbide matrix composite, particularly prepare the method for carbon/carbon fiber reinforced silicon carbide matrix composite fast with chemical liquids vapour-phase pyrolysis matrix precursor.
Background technology
The patent No. is friction means and the manufacture method thereof that the Chinese patent of CN97199764.0 has been introduced a kind of carbon/carbon fiber reinforced silicon carbide matrix composite, and this invention is particularly useful for the brake material manufacturing of rail vehicle and automobile.This method is to obtain first kind of phase of RESEARCH OF PYROCARBON by the chemical vapors infiltration near fortifying fibre, obtain second kind of carbon or ceramic infusibility phase by a kind of liquid phase matrix of pyrolysis precursor at least in part, and obtaining silicon carbide by forming salicide processes, matrix is included near each or the described friction surface at least.This carbon/carbon fiber reinforced silicon carbide matrix composite preferable range is as follows, promptly near the formation by volume each or described friction surface is at least at least: 15～35% carbon fiber, 10～55% contain RESEARCH OF PYROCARBON matrix phase, second kind of matrix phase of 2～30% refractory materials, and 10～35% silicon carbide.
This method has following deficiency: obtain uniform tissue near being difficult to be controlled at each or described friction surface, tissue repeatability is relatively poor, causes in the future the frictional behaviour of each or described friction surface stable inadequately; Matrix precursor utilization ratio is low, and less than 5%, the exhaust emission amount is big; In addition, obtain first kind of phase of RESEARCH OF PYROCARBON by the chemical vapors infiltration, obtain second kind of carbon or ceramic infusibility phase by a kind of liquid phase matrix of pyrolysis precursor at least in part, and by forming salicide processes acquisition silicon carbide, need to concentrate the matrix precursor, complicated process of preparation, preparation cycle reached more than one month.
Summary of the invention
The deficiency that prior art matrix precursor utilization ratio is low in order to overcome, preparation cycle is long the invention provides a kind of method for preparing carbon/carbon fiber reinforced silicon carbide matrix composite, can be fast, the low-cost toughness reinforcing carbon/carbon fiber reinforced silicon carbide matrix composite of carbon fiber enhancing of making.
The technical solution adopted for the present invention to solve the technical problems is: a kind of method for preparing carbon/carbon fiber reinforced silicon carbide matrix composite, it is characterized in that, and comprise the steps:
1) be that 1～50mm, density are 0.3g/cm with thickness
3Two-dimensional quadrature continuous carbon fibre and the even sheet material preformed objects of short carbon fiber shuffling puncture felt strengthen body, the even sheet material preformed objects of perhaps full carbon cloth puncture knitted body strengthens body, is placed in the baking oven, after two hours, the cleaning preformed objects strengthens the surface 80～100 ℃ of oven dry;
2) two copper electrodes are adjusted on the same horizontal plane and are connected with power supply respectively, straight graphite block around on each copper electrode, respectively placing one, on graphite block, take and put preformed objects enhancing body, strengthen on the body in preformed objects, the graphite block corresponding position of placing is placed identical graphite block more earlier, and graphite cushion block and preformed objects enhancing body is fastening;
3) in the sediment chamber of placing preformed objects enhancing body, inject the precursor hexamethyldisilazane, make liquid level surpass preformed objects and strengthen 5～10 millimeters of bodies, fed nitrogen continuously 10～30 minutes for the sediment chamber, get rid of the deposition room air, connect cooling water recirculation system, connect power supply heating preformed objects and strengthen body, evenly be raised to 700～900 ℃ at 10 minutes by room temperature, constantly inject the hexamethyldisilazane precursor during this time, and keep liquid level to surpass 5～10 millimeters of preformed objects enhancing bodies, be incubated 0.5～15 hour;
4) powered-down is cooled to room temperature naturally, reclaims sediment chamber's residue hexamethyldisilazane precursor, takes out product.
The invention has the beneficial effects as follows, owing to adopted hexamethyldisilazane to strengthen the body heating of directly switching on as matrix precursor and preformed objects, chemical liquids vapour-phase pyrolysis matrix precursor obtains two kinds of matrix phases of carbon-silicon carbide simultaneously, and preparation time obtains being reduced to more than month 0.5～15 hour of a kind of phase of RESEARCH OF PYROCARBON from the infiltration of prior art chemical vapors; And technology is simple, and the one-time continuous deposition cycle is promptly finished preparation; Utilize again because precursor is recyclable, so the precursor utilization ratio brings up to 50% from a kind of phase of prior art chemical vapors infiltration acquisition RESEARCH OF PYROCARBON less than 5%, precursor hexamethyldisilazane itself is pollution-free, non-stimulated, human body is not had injury, and its degradation production compared with prior art environmental pollution is little.
The present invention is further described below in conjunction with drawings and Examples.
Description of drawings
Accompanying drawing is the method preparation facilities synoptic diagram that the present invention prepares carbon/carbon fiber reinforced silicon carbide matrix composite
Among the figure, 1-copper electrode, 2-graphite block, 3-preformed objects strengthens body 4-storage tank 5-pump 6-sediment chamber 7-cooling water tank, 8-power supply
Embodiment
Embodiment 1:
Step 1: strengthen body and prepare.Check that density is greater than 0.3g/cm
3Two-dimensional quadrature continuous carbon fibre and the even sheet material preformed objects of short carbon fiber shuffling puncture felt strengthen body, thickness 10mm, width 10mm, length 100mm.Do not allow and damage greater than 4mm.80 ℃ of oven dry were placed on the clean arbitrarily smooth iron plate after two hours in baking oven, brushed away surface dirt with hairbrush.
Step 2: prepare the sediment chamber.Steel plate system deposition chamber wall interlayer checks by water quench whether water circulation system has leakage, cleaning deposition chamber.
Step 3: strengthen body and install.Copper electrode is electrically connected with power supply 8 respectively, and two copper electrodes, 1 working face must keep level, and on same horizontal plane.Straight graphite cushion block 2 around the horizontal positioned on copper electrode 1 is laid preformed objects then and is strengthened body 3, lays graphite cushion block 2 on it again, allows preformed objects strengthen body 3 and is in the centre of two-layer graphite cushion block up and down.Clamp two-layer graphite cushion block 2 and preformed objects therebetween and strengthen body 3.Be about 2～3 millimeters with the vernier caliper measurement draught simultaneously.Can select the slip gauge check draught of suitable thickness for use.Because preformed objects strengthens the ununiformity of body 3 sheet materials braiding, draught can only be regulated within the specific limits.Thermopair is installed.Touch the thermopair tip with hand, heat up, observe thermometer and whether heat up, whether work with the check thermopair by body temperature.Then with strict half place that inserts preformed objects enhancing body thickness, thermopair tip.
Step 4: chemical liquids vapour-phase pyrolysis matrix precursor.
From storage tank 4, in sediment chamber 6, pump into the hexamethyldisilazane precursor, make liquid level surpass 5 millimeters at the top that preformed objects strengthens the even sheet material of body slightly with pump 5.Write down the height of liquid level meter then.
Feed nitrogen protection gas to sediment chamber 6, the logical nitrogen of non-stop run 10 minutes is as the criterion so that the most air in the sediment chamber are discharged.
Densification deposition: connect cooling water tank 7 logical water coolants, connect power supply 8 energising heating preformed objects and strengthen body 3, evenly be raised to 700 ℃ in 10 minutes by room temperature, the mode that constantly pumps into from storage tank 4 by liquor pump in the densification deposition is replenished precursor, preferably remains to original liquid level.Because liquid level boiling, liquid level constantly fluctuates, and can be under 8 the situation of cutting off the electricity supply correctly judges fuel head, so that it is correct to add the precursor amount.Depositing time 0.5 hour.Forbid water and hydrous matter to enter in the sediment chamber 6 in the deposition.
Because it is conductors that preformed objects strengthens body 3 even sheet materials, be heated in the energising, preformed objects strengthens body 3 even sheet materials and is immersed in the precursor liquid, thus preformed objects enhancing body plate 3 materials by the center to outside surface formation temperature gradient, core temperature is higher than outside surface.Hexamethyldisilazane precursor liquid strengthens body 3 inside by penetrating into, and precursor liquid moment becomes gas, and becomes RESEARCH OF PYROCARBON, SiC and Si in the high-temperature zone pyrolysis
3N
4Mixture stay inside.Along with the prolongation of time, RESEARCH OF PYROCARBON, SiC and Si
3N
4Mixture strengthen body 3 even sheet material inside by preformed objects gradually and expand to external sediment, final sedimentation products is covered with in the space of whole preformed objects enhancing body 3 even sheet materials.
Step 5: take out product.Cut off propulsion source, residue hexamethyldisilazane precursor is discharged to storage tank 4 in the cooling back naturally.The cooling back is from taking out the finished product of densification to sediment chamber 6.
Embodiment 2:
Step 1: strengthen body and prepare.Check that density is greater than 0.3g/cm
3The even sheet material preformed objects of full carbon cloth puncture knitted body strengthen body, thickness 30mm, width 100mm, length 1000mm.Do not allow and damage greater than 4mm.In baking oven, dry after two hours in 90 ℃ of air, be placed on the clean arbitrarily smooth iron plate, brush away surface dirt with hairbrush.
Step 2: prepare the sediment chamber.Steel plate system deposition chamber wall interlayer checks by water quench whether water circulation system has leakage, cleaning deposition chamber.
Step 3: strengthen body and install.Copper electrode is electrically connected with power supply 8 respectively, and two copper electrodes, 1 working face must keep level, and on same horizontal plane.Straight graphite cushion block 2 around the horizontal positioned on copper electrode 1 is laid preformed objects then and is strengthened body 3, lays graphite cushion block 2 on it again, allows preformed objects strengthen body 3 and is in the centre of two-layer graphite cushion block up and down.Clamp two-layer graphite cushion block 2 and preformed objects therebetween and strengthen body 3.Be about 3～4 millimeters with the vernier caliper measurement draught simultaneously.Can select the slip gauge check draught of suitable thickness for use.Because preformed objects strengthens the ununiformity of body 3 sheet materials braiding, draught can only be regulated within the specific limits.Thermopair is installed.Touch the thermopair tip with hand, heat up, observe thermometer and whether heat up, whether work with the check thermopair by body temperature.Then with strict half place that inserts preformed objects enhancing body thickness, thermopair tip.
Step 4: chemical liquids vapour-phase pyrolysis matrix precursor.
From storage tank 4, in sediment chamber 6, pump into the hexamethyldisilazane precursor, make liquid level surpass 8 millimeters at the top that preformed objects strengthens the even sheet material of body slightly with pump 5.Write down the height of liquid level meter then.
Feed nitrogen protection gas to sediment chamber 6, the logical nitrogen of non-stop run 20 minutes is as the criterion so that the most air in the sediment chamber are discharged.
Densification deposition: connect cooling water tank 7 logical water coolants, connect power supply 8 energising heating preformed objects and strengthen body 3, evenly be raised to 800 ℃ in 10 minutes by room temperature, the mode that constantly pumps into from storage tank 4 by liquor pump in the densification deposition is replenished precursor, preferably remains to original liquid level.Because liquid level boiling, liquid level constantly fluctuates, and can be under 8 the situation of cutting off the electricity supply correctly judges fuel head, so that it is correct to add the precursor amount.Depositing time 8 hours.Forbid water and hydrous matter to enter in the sediment chamber 6 in the deposition.
Step 5: take out product.Cut off propulsion source, residue hexamethyldisilazane precursor is discharged to storage tank 4 in the cooling back naturally.The cooling back is from taking out the finished product of densification to sediment chamber 6.
Embodiment 3:
Step 1: strengthen body and prepare.Check that density is greater than 0.3g/cm
3The even sheet material preformed objects of full carbon cloth puncture knitted body strengthen body, thickness 50mm, width 500mm, length 2000mm.Do not allow and damage greater than 4mm.In baking oven, dry after two hours in 100 ° of C air, be placed on the clean arbitrarily smooth iron plate, brush away surface dirt with hairbrush.
Step 2: prepare the sediment chamber.Steel plate system deposition chamber wall interlayer checks by water quench whether water circulation system has leakage, cleaning deposition chamber.
Step 3: strengthen body and install.Copper electrode is electrically connected with power supply 8 respectively, and two copper electrodes, 1 working face must keep level, and on same horizontal plane.Straight graphite cushion block 2 around the horizontal positioned on copper electrode 1 is laid preformed objects then and is strengthened body 3, lays graphite cushion block 2 on it again, allows preformed objects strengthen body 3 and is in the centre of two-layer graphite cushion block up and down.Clamp two-layer graphite cushion block 2 and preformed objects therebetween and strengthen body 3.Be about 4～6 millimeters with the vernier caliper measurement draught simultaneously.Can select the slip gauge check draught of suitable thickness for use.Because preformed objects strengthens the ununiformity of body 3 sheet materials braiding, draught can only be regulated within the specific limits.Thermopair is installed.Touch the thermopair tip with hand, heat up, observe thermometer and whether heat up, whether work with the check thermopair by body temperature.Then with strict half place that inserts preformed objects enhancing body thickness, thermopair tip.
Step 4: chemical liquids vapour-phase pyrolysis matrix precursor.
From storage tank 4, in sediment chamber 6, pump into the hexamethyldisilazane precursor, make liquid level surpass 10 millimeters at the top that preformed objects strengthens the even sheet material of body slightly with pump 5.Write down the height of liquid level meter then.
Feed nitrogen protection gas to sediment chamber 6, the logical nitrogen of non-stop run 30 minutes is as the criterion so that the most air in the sediment chamber are discharged.
Densification deposition: connect cooling water tank 7 logical water coolants, connect power supply 8 energising heating preformed objects and strengthen body 3, evenly be raised to 900 ℃ in 10 minutes by room temperature, the mode that constantly pumps into from storage tank 4 by liquor pump in the densification deposition is replenished precursor, preferably remains to original liquid level.Because liquid level boiling, liquid level constantly fluctuates, and can be under 8 the situation of cutting off the electricity supply correctly judges fuel head, so that it is correct to add the precursor amount.Depositing time 15 hours.Forbid water and hydrous matter to enter in the sediment chamber 6 in the deposition.
Step 5: take out product.Cut off propulsion source, residue hexamethyldisilazane precursor is discharged to storage tank 4 in the cooling back naturally.The cooling back is from taking out the finished product of densification to sediment chamber 6.
Claims (1)
1. a method for preparing carbon/carbon fiber reinforced silicon carbide matrix composite is characterized in that, comprises the steps:
1) be that 1～50mm, density are 0.3g/cm with thickness
3Two-dimensional quadrature continuous carbon fibre and the even sheet material preformed objects of short carbon fiber shuffling puncture felt strengthen body, the even sheet material preformed objects of perhaps full carbon cloth puncture knitted body strengthens body, is placed in the baking oven, after two hours, the cleaning preformed objects strengthens the surface 80～100 ℃ of oven dry;
2) two copper electrodes are adjusted on the same horizontal plane and are connected with power supply respectively, straight graphite block around on each copper electrode, respectively placing one, on graphite block, take and put preformed objects enhancing body, strengthen on the body in preformed objects, the graphite block corresponding position of placing is placed identical graphite block more earlier, and graphite cushion block and preformed objects enhancing body is fastening;
3) in the sediment chamber of placing preformed objects enhancing body, inject the precursor hexamethyldisilazane, make liquid level surpass preformed objects and strengthen 5～10 millimeters of bodies, fed nitrogen continuously 10～30 minutes for the sediment chamber, get rid of the deposition room air, connect cooling water recirculation system, connect power supply heating preformed objects and strengthen body, evenly be raised to 700～900 ℃ at 10 minutes by room temperature, constantly inject the hexamethyldisilazane precursor during this time, and keep liquid level to surpass 5～10 millimeters of preformed objects enhancing bodies, be incubated 0.5～15 hour;
4) powered-down is cooled to room temperature naturally, reclaims sediment chamber's residue hexamethyldisilazane precursor, takes out product.
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| CNB2006100430344A CN100372809C (en) | 2006-06-27 | 2006-06-27 | Process for preparation of carbon/carbon-silicon carbide composites by liquid-gas phase pyrolysis of matrix precursor |
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| CNB2006100430344A CN100372809C (en) | 2006-06-27 | 2006-06-27 | Process for preparation of carbon/carbon-silicon carbide composites by liquid-gas phase pyrolysis of matrix precursor |
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| CN101260005B (en) * | 2008-01-09 | 2010-06-02 | 西安航天复合材料研究所 | Method for preparing carbon/carbon/silicon carbide composite material |
| CN105016760B (en) * | 2015-07-09 | 2017-04-05 | 西北工业大学 | A kind of preparation method of the modified C/C composites of superhigh temperature ceramics |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1237950A (en) * | 1996-10-14 | 1999-12-08 | 航空发动机的结构和研究公司 | Friction element in composite carbon/carbon-silicon carbide material and method for manufacturing same |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1237950A (en) * | 1996-10-14 | 1999-12-08 | 航空发动机的结构和研究公司 | Friction element in composite carbon/carbon-silicon carbide material and method for manufacturing same |
Non-Patent Citations (1)
| Title |
|---|
| C/C-SiC材料的快速制备及显微结构研究. 王继平，金志浩，钱军民，乔冠军.稀有金属材料与工程，第35卷第2期. 2006 * |
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