CN100441741C - Preparation method of carbon/carbon composite material and phosphate anti oxidation coating for same - Google Patents
Preparation method of carbon/carbon composite material and phosphate anti oxidation coating for same Download PDFInfo
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- CN100441741C CN100441741C CNB2006100896170A CN200610089617A CN100441741C CN 100441741 C CN100441741 C CN 100441741C CN B2006100896170 A CNB2006100896170 A CN B2006100896170A CN 200610089617 A CN200610089617 A CN 200610089617A CN 100441741 C CN100441741 C CN 100441741C
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Abstract
A neotype phosphate inoxidzable coating of carbon(C) or its complex materials, the preparation process was as follows: (1) The preparation of C and its complex materials: Taking their precast objects as long stapled needling blanket, C and its complex materials were prepared with chemical vapour deposition process. (2) Interface design and component matchiong of coat: Phosphate including manganese phosphate, tribasic zinc phosphate and chromium phosphate etc. was selected as main phas. Aluminium oxide and zinc oxide or aluminium chloride and zinc chloride was taken as agglomerant. Distilled water solution of phosphoric acid with a mass percent of 50% was used as solvent. (3) The preparation process of coat: (1)Craft of slurry brushing: Firstly, distilled water solution of phosphoric acid was prepared. Then, each component was added ordinally into solution from little amount to excessive amount. After mixing equably, slurry was coated equably onto the surface of materials. (2)Craft of high temperature sintering: Coated materials were heated up to 300deg.C in 1 to 2 hours, and temperature should be kept for 2 to 4 hour. Then, materials were heated slowly up to 700-900deg.C in 2 to 3 hours and were sintered in high temperature for 2 to 4 hours.
Description
(1) technical field:
The invention provides the preparation method of the novel phosphate anti oxidation coating of a kind of carbon/carbon compound material, belong to the carbon/carbon compound material technical field.
(2) background technology:
The two-phase carbon body material that carbon/carbon (C/C) matrix material is made up of carbon-fiber reinforced carbon matter matrix, it is widely used as high-temperature structural material with its excellent high-temperature behavior.Yet under the Working environment of aerobic, when temperature is higher than 400 ℃, oxidation will take place in the C/C matrix material, thereby cause its mechanical property to descend rapidly, particularly influence is even more serious for the parts that use repeatedly, will influence the security and the reliability of its brake as the oxidation of aircraft brake flange, even cause brake to be lost efficacy, consequence is hardly imaginable.Since 1934, National Carbon Co.Applied for first part about since the patent of carbon material high-temp antioxidizing the history in more than 70 year having been arranged.C/C composite material antioxidation research has at present also had development at full speed, and anti-oxidation method is progressive and perfect constantly, but the ubiquity preparation cost is higher at present, preparation technology is complicated and problem that can not reparation property.Therefore, the low-cost coating technology of C/C matrix material not only has important significance for theories, but also has very important practical significance.
(3) summary of the invention:
The preparation method of the novel phosphate anti oxidation coating of a kind of carbon/carbon compound material of the present invention, its main purpose provide that a kind of preparation cost is lower, the preparation method of the better simply novel phosphate anti oxidation compound coating of preparation technology.This coating is even compact very, and after 700 ℃ of constant temperature oxidation tests, oxidative mass loss is 0.7% only, soak seawater constant temperature oxidation experiment and thermal shock experiment after, the anti-aging capability of coating does not almost change.
The preparation method of the novel phosphate anti oxidation coating of a kind of carbon/carbon compound material of the present invention, its technical scheme is divided into following a few part: the preparation of C/C material, the INTERFACE DESIGN of coating and composition
Proportioning, the preparation of coating.Its preparation method as shown in Figure 1.
(1) preparation of C/C material:
The precast body of the used C/C matrix material of the present invention is the macrofiber Nomex, and adopts that the chemical vapor deposition (CVD) method is prepared to form, and its density is 1.72g/cm
3It is 10 * 10 * 10mm that material is all made specification
3Shape, and to the surface treatment of its chamfering of polishing.
(2) INTERFACE DESIGN of coating and composition proportion:
It is principal phase that the present invention selects phosphoric acid salt such as manganous phosphate, zinc phosphate, aluminum phosphate, Plessy's green respectively for use; With oxide compounds such as aluminum oxide, zinc oxide, perhaps muriate such as aluminum chloride, zinc chloride is as binding agent; And with phosphoric acid is that 50% distilled water solution is a solvent by mass percentage.Each material is chemical pure.The present invention has chosen five groups of raw materials that different phosphoric acid salt are the preparation coating, shown in the following tabulation 1.
Five groups of different phosphate coating proportionings of table 1
Annotate: each number is mass percent (wt%) in the table; A～E represents the sequence number of five kinds of coatings, and the ratio of aluminum chloride and zinc chloride and aluminum oxide and zinc oxide is 1: 1.
(3) preparation method of coating:
1. slip brushing technique:
Proportioning according to the aqueous solution of five kinds of phosphate coating materials shown in the table 1 and phosphoric acid, prepare the distilled water solution of phosphoric acid earlier, the component that adds aluminum oxide and zinc oxide or aluminum chloride and zinc chloride then, few from measuring successively again to the multicomponent order adding of amount phosphate component, stir.With brush slip is applied to material surface equably then, treats that it dries 2～4 hours (h) naturally and brushes in air, repeat 4～6 times.
2. high-sintering process:
The material that coats coating at 1～2h internal heating to 300 ℃, and is incubated 2～4h, in 2～3h, slowly is heated to 700～900 ℃ then, and makes material at high temperature sintering 2～4h.
Material heat treatment equipment is made up of rotary type resistance furnace, temperature regulator, under meter etc. among the present invention, and its synoptic diagram as shown in Figure 2.Nitrogengas cylinder connects a gas meter, and by its control nitrogen flow rate, feeds a silica tube of rotary type resistance furnace workspace then, with protecting materials.The temperature of workspace is by a thermocouple measurement, and by temperature regulator according to the temperature control heating of being surveyed.
In sum, after executing according to above-mentioned each processing step operation, the novel phosphate anti oxidation coating of carbon/carbon compound material of the present invention just can prepare to be finished.
The preparation method of the novel phosphate anti oxidation coating of a kind of carbon/carbon compound material of the present invention, its advantage is: preparation technology is simple, and cost is low, implements easily, and the anti-oxidation performance height of coating has higher resistance to corrosion, and thermal shock resistance is good.
To coating carry out material that performance test: a. will prepare coating 700 ℃ carry out constant temperature static oxidation 100h after, record oxidative mass loss less than 1%, the anti-oxidation performance of coating is higher; B. after soaking seawater constant temperature oxidation experiment, the anti-oxidation performance of coating does not almost change, thereby coating has higher resistance to corrosion; C. material is after 40～60 times the thermal shock experiment of circulating under 800 ℃, and recording material rate of weight loss after this thermal cycling is 0.9% only, and thermal shock performance of coatings is higher.
Shown in Figure 3 is the SEM photo of 700 ℃ of following oxidation 100h of coating front and back; as can be seen from the figure; the oxidation Front-coating mirror very evenly, fine and close (Fig. 3 a); and behind 700 ℃ of following oxidation 100h; though there is a small amount of tiny crack on some zone-coating surface; but cracks has the oxide compound of vitreous state to fill, and makes matrix C/C matrix material still be subjected to protection (Fig. 3 b) significantly.
(4) description of drawings:
Fig. 1. the coating production synoptic diagram
Fig. 2. the Equipment for Heating Processing synoptic diagram
Microscopic appearance figure before Fig. 3 (a) .D2 group material oxidation
Microscopic appearance figure after Fig. 3 (b) .D2 group material oxidation
Fig. 4. the temperature program of coating preparation
Nomenclature:
A.T is a Kelvin's temperature, and t is the time
(5) embodiment:
The preparation method of the novel phosphate anti oxidation coating of a kind of carbon/carbon compound material of the present invention, its processing step is as follows:
The preparation of a.C/C material
The precast body of the used C/C matrix material of the present invention is the macrofiber Nomex, and adopts that the chemical vapor deposition (CVD) method is prepared to form, and its density is 1.72g/cm
3。Material is made 10 * 10 * 10mm
3Specification, emery paper hand sand with 400 coarse sands, make it have certain roughness, and with its chamfering, and with dehydrated alcohol as solvent Ultrasonic Cleaners cleaning material, and then material put into loft drier, take out 5 hours (h) backs of freeze-day with constant temperature under 100 ℃ condition, in order to applying coating.
B. the INTERFACE DESIGN of coating and composition proportion
Chosen the phosphate coating of five kinds of different proportionings: it is principal phase that each group is got phosphoric acid salt such as manganous phosphate, calcium phosphate zinc, aluminum phosphate, Plessy's green respectively; With oxide compounds such as aluminum oxide, zinc oxide, perhaps muriate such as aluminum chloride, zinc chloride is as binding agent, and is that 50% distilled water solution is a solvent by mass percentage with phosphoric acid.Prepare coating according to proportioning as shown in table 1.
C. the preparation technology of coating
● the slip brushing technique
Measure each component with electronic balance in various ratios as shown in table 1, prepare the distilled water solution of phosphoric acid earlier, the component of aluminum oxide that add-on is few and zinc oxide or aluminum chloride and zinc chloride then, many phosphate component of add-on again, component of every adding is all wanted earlier fully stirring.With brush slip is applied to material surface equably then, treat that it dries 2～4h naturally in air after, be coated with one deck again, repeat 4～6 times, have the layer of even white powder to be advisable up to the surface.
● high-sintering process
The material that coats coating packed into by numbering burn in the boat, put into the rotary type resistance furnace,,, when temperature rises to 300 ℃, feed nitrogen therebetween according to temperature program heating shown in Figure 4.For volatile component can fully be overflowed when the heating, and guarantee that coating can not ftracture because of volatilization, temperature rise rate is unsuitable too fast, and is same, and rate of temperature fall is also wanted slowly.
Embodiment one: choose aluminum phosphate, zinc phosphate, aluminum chloride and zinc chloride as effective constituent, the solution of using distilled water and phosphoric acid is as solvent, and is as shown in table 2.
Table 2 embodiment one each composition proportion
Annotate: each number average is mass percent (wt%) in the table
A. slip brushing technique
Measure each component with electronic balance in predetermined various ratios, each raw material is stirred into slip after, with brush it is coated in material surface equably, after treating that it dries 2h naturally in air, be coated with one deck again, repeat 4 times, have the layer of even white powder to be advisable up to the surface.
B. high-sintering process
The material that coats coating packed into by numbering burn in the boat, put into the rotary type resistance furnace, according to temperature program heating shown in Figure 4.
Embodiment two: choose aluminum phosphate, zinc phosphate, manganous phosphate, aluminum chloride and zinc chloride as effective constituent, the solution of using distilled water and phosphoric acid is as solvent, and is as shown in table 3.
Table 3 embodiment two each composition proportion
Annotate: each number average is mass percent (wt%) in the table
A. slip brushing technique
Measure each component with electronic balance in predetermined various ratios, each raw material is stirred into slip after, with brush it is coated in material surface equably, after treating that it dries 2h naturally in air, be coated with one deck again, repeat 5 times, have the layer of even white powder to be advisable up to the surface.
B. high-sintering process
The material that coats coating packed into by numbering burn in the boat, put into the rotary type resistance furnace, according to temperature program heating shown in Figure 4.
Embodiment three: choose aluminum phosphate, Plessy's green, aluminum oxide and zinc oxide as effective constituent, the solution of using distilled water and phosphoric acid is as solvent, and is as shown in table 4.
Table 4 embodiment three each composition proportion
Annotate: each number average is mass percent (wt%) in the table
A. slip brushing technique
Measure each component with electronic balance in predetermined various ratios, each raw material is stirred into slip after, with brush it is coated in material surface equably, after treating that it dries 2h naturally in air, be coated with one deck again, repeat 6 times, have the layer of even white powder to be advisable up to the surface.
B. high-sintering process
The material that coats coating packed into by numbering burn in the boat, put into the rotary type resistance furnace, according to temperature program heating shown in Figure 4.
Embodiment four: choose aluminum phosphate, zinc phosphate, aluminum oxide and zinc oxide as effective constituent, the solution of using distilled water and phosphoric acid is as solvent, and is as shown in table 5.
Table 5 embodiment four each composition proportion
Annotate: each number average is a mass percent in the table
A. slip brushing technique
Measure each component with electronic balance in predetermined various ratios, each raw material is stirred into slip after, with brush it is coated in material surface equably, after treating that it dries 3h naturally in air, be coated with one deck again, repeat 5 times, have the layer of even white powder to be advisable up to the surface.
B. high-sintering process
The material that coats coating packed into by numbering burn in the boat, put into the rotary type resistance furnace, according to temperature program heating shown in Figure 4.
Embodiment five: choose aluminum phosphate, zinc phosphate, manganous phosphate, aluminum oxide and zinc oxide as effective constituent, the solution of using distilled water and phosphoric acid prepares slurry as solvent by weight percent as shown in table 6.
Table 6 embodiment five each composition proportion
Annotate: each number average is mass percent (wt%) in the table
A. slip brushing technique
Measure each component with electronic balance in predetermined various ratios, each raw material is stirred into slip after, with brush it is coated in material surface equably, after treating that it dries 3h naturally in air, be coated with one deck again, repeat 6 times, have the layer of even white powder to be advisable up to the surface.
B. high-sintering process
The material that coats coating packed into by numbering burn in the boat, put into the rotary type resistance furnace, according to temperature program heating shown in Figure 4.
Claims (1)
1, the preparation method of the novel phosphate anti oxidation coating of a kind of carbon/carbon compound material, it is characterized in that: the processing step of its preparation method is as follows:
(1) preparation of C/C material:
The precast body of C/C matrix material is the macrofiber Nomex, and adopts chemical Vapor deposition process to be prepared from, and its density is 1.72g/cm
3It is 10 * 10 * 10mm that material is all made specification
3Shape, and to the surface treatment of its chamfering of polishing;
(2) INTERFACE DESIGN of coating and composition proportion:
Selecting manganous phosphate, zinc phosphate, aluminum phosphate, Plessy's green respectively for use is principal phase; With aluminum oxide and zinc oxide, perhaps aluminum chloride and zinc chloride are as binding agent; And with phosphoric acid is that 50% distilled water solution is a solvent by mass percentage; Each material is chemical pure; The present invention has chosen the raw material of different phosphoric acid salt for the preparation coating, and the mass percent proportioning of the phosphate coating composition that these are different is as follows:
A: solvent 70%, aluminum phosphate 5～15%, zinc phosphate 5～15%, aluminum chloride+zinc chloride 10%;
B: solvent 60%, aluminum phosphate 5～15%, zinc phosphate 10%, manganous phosphate 5～15%, aluminum chloride+zinc chloride 10%;
D: solvent 70%, aluminum phosphate 5～15%, zinc phosphate 5～15%, aluminum oxide+zinc oxide 10%;
E: solvent 60%, aluminum phosphate 5～15%, zinc phosphate 10%, manganous phosphate 5～15%, aluminum oxide+zinc oxide 10%.
(3) preparation method of coating:
1. slip brushing technique:
Proportioning according to the aqueous solution of listed phosphate coating material of step (2) and phosphoric acid, prepare the distilled water solution of phosphoric acid earlier, the component that adds aluminum oxide and zinc oxide or aluminum chloride and zinc chloride then, few from measuring successively again to the multicomponent order adding of amount phosphate component, stir; With brush slip is applied to material surface equably then, treats that it dries brushing again in 2～4 hours naturally in air, repeat 4～6 times;
2. high-sintering process:
The material that coats coating at 1～2 hour internal heating to 250 ℃, and is incubated 2～4 hours, in 2～3 hours, slowly is heated to 700～900 ℃ then, and made the material at high temperature sintering 2～4 hours; Its material hot treatment equipment is made up of rotary type resistance furnace, temperature regulator, under meter etc.; Nitrogengas cylinder connects a gas meter, and by its control nitrogen flow rate, feeds a silica tube of rotary type resistance furnace workspace then, with protecting materials; The temperature of workspace is by a thermocouple measurement, and by temperature regulator according to the temperature control heating of being surveyed.
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| CNB2006100896170A CN100441741C (en) | 2006-07-06 | 2006-07-06 | Preparation method of carbon/carbon composite material and phosphate anti oxidation coating for same |
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| CNB2006100896170A CN100441741C (en) | 2006-07-06 | 2006-07-06 | Preparation method of carbon/carbon composite material and phosphate anti oxidation coating for same |
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| CN100441741C true CN100441741C (en) | 2008-12-10 |
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Families Citing this family (4)
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| CN102424574B (en) * | 2011-08-31 | 2013-01-30 | 湖北三江航天江北机械工程有限公司 | Carbon fiber reinforced phosphate composite material forming process |
| CN102503562B (en) * | 2011-11-23 | 2013-04-10 | 陕西科技大学 | Preparation method of carbon/carbon composite material anti-oxidation phosphate glass coating |
| CN104589724B (en) * | 2014-12-24 | 2017-06-13 | 中国建筑材料科学研究总院 | Suture stratiform flexible insulant material and preparation method thereof |
| CN104891480A (en) * | 2015-05-28 | 2015-09-09 | 中国科学院山西煤炭化学研究所 | Preparation method for antioxidative graphite material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4292345A (en) * | 1980-02-04 | 1981-09-29 | Kolesnik Mikhail I | Method of protecting carbon-containing component parts of metallurgical units from oxidation |
| US4439491A (en) * | 1982-11-18 | 1984-03-27 | Great Lakes Carbon Corporation | Oxidation retardant for graphite |
| EP0677499A2 (en) * | 1994-03-18 | 1995-10-18 | The B.F. Goodrich Company | Inhibition of catalyzed oxidation of carbon-carbon composites |
| CN1162298A (en) * | 1994-11-04 | 1997-10-15 | 推进欧洲公司 | Method for oxidation protection of articles made of carbon-containing composite material |
| US20040038043A1 (en) * | 1999-03-04 | 2004-02-26 | Ilan Golecki | Fluidizing oxidation protection systems |
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2006
- 2006-07-06 CN CNB2006100896170A patent/CN100441741C/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4292345A (en) * | 1980-02-04 | 1981-09-29 | Kolesnik Mikhail I | Method of protecting carbon-containing component parts of metallurgical units from oxidation |
| US4439491A (en) * | 1982-11-18 | 1984-03-27 | Great Lakes Carbon Corporation | Oxidation retardant for graphite |
| EP0677499A2 (en) * | 1994-03-18 | 1995-10-18 | The B.F. Goodrich Company | Inhibition of catalyzed oxidation of carbon-carbon composites |
| CN1162298A (en) * | 1994-11-04 | 1997-10-15 | 推进欧洲公司 | Method for oxidation protection of articles made of carbon-containing composite material |
| US20040038043A1 (en) * | 1999-03-04 | 2004-02-26 | Ilan Golecki | Fluidizing oxidation protection systems |
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