CN109233289A - A kind of preparation method of modified silicon rubber sealing element - Google Patents
A kind of preparation method of modified silicon rubber sealing element Download PDFInfo
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- CN109233289A CN109233289A CN201811032273.9A CN201811032273A CN109233289A CN 109233289 A CN109233289 A CN 109233289A CN 201811032273 A CN201811032273 A CN 201811032273A CN 109233289 A CN109233289 A CN 109233289A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/011—Nanostructured additives
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Abstract
The invention discloses a kind of preparation methods of modified silicon rubber sealing element, are related to sealing member material technical field.The present invention is modified processing to soft graphite, improves the ageing resistance of silicon rubber；Modified soft graphite can solve the problem of nano aluminium oxide, silicon carbide are ineffective in conjunction with silicon rubber, raw material effect is unable to give full play simultaneously；During methyl vinyl silicone rubber carries out sulfidization molding, with the unsaturated bond in silicon rubber part polyaddition reaction can occur for fatty alcohol polyoxypropylene ether, be obviously improved the physical properties such as tensile strength, the impact resistant strength of methyl vinyl silicone rubber；Silicone rubber seal prepared by the present invention, impact resistance, good seal performance, excellent physical properties, simple process is efficient, is suitble to industrialized production.
Description
Technical field:
The present invention relates to sealing member material technical fields, and in particular to a kind of preparation method of modified silicon rubber sealing element.
Background technique:
Silicon rubber be it is a kind of have both inorganic and organic nature macromolecular material, molecular backbone is by silicon atom and oxygen
Atom alternately forms, and side chain is be connected with silicon atom hydrocarbon or replaces hydrocarbon organic group, this group can be methyl,
Unsaturated ethylene alkenyl or other organic groups, this unsaturated molecular structure make silicon rubber have excellent heat-resistant aging and
Weatherable, UV resistant and ozone corrosion.The toughness of strand is larger, and the interaction of molecule interchain is weaker, these knots
Structure feature keeps vulcanized rubber soft and flexible, but physical property is poor.
Summary of the invention:
Technical problem to be solved by the present invention lies in provide it is a kind of stretch, bending strength it is high, impact resistance, physical property is excellent
The preparation method of different modified silicon rubber sealing element.
The following technical solution is employed for the technical problems to be solved by the invention to realize:
A kind of preparation method of modified silicon rubber sealing element, comprising the following steps:
(1) methyl vinyl silicone rubber is put into mixer the 10-20min that plasticates；
(2) by the methyl vinyl silicone rubber after plasticating, reinforcing agent, activating agent, dispersing agent and anti-aging agent, double roller is added and opens
In mill, it is heated with stirring to 350-360 DEG C, mixing speed 800-900r/min, reacts 30-50min, slow cooling to 80-
90 DEG C, mixture sieving sorting obtains sieving product；
(3) the sieving product of step 2 is injected in seal mold appropriate, vulcanizing agent and fatty alcohol polyoxypropylene is added
Ether suppresses sealing element type embryo, and sealing element type embryo, which is immersed in the mixed liquor of 4,4'- dichloro diphenyl sulfone and tetraethyl orthosilicate, to be consolidated
Change reaction, reaction time 1-2h；
(4) the sealing element curing type embryo of step 3 is put into high pressure-temperature sintering furnace and carries out pressurized, heated molding and vulcanization,
Reacting furnace temperature is 200-300 DEG C, pressure 80-90MPa, is slowly pressurizeed, and after keeping high pressure-temperature reaction 20-40min, is carried out
Temperature fall and decompression are until consistent with external environment；
(5) sealing element molding in step 4 is put into inert gas reacting furnace and is heated to 65-70 DEG C, soaking time 15-
20min, the disodium bicarbonate solution for being 7.5% to sealing element sprinkling mass fraction, carries out stripper member process, obtains in sealing element
Between product；
(6) product among the sealing element of step 5 are placed on vulcanizing press, are further vulcanized, obtains modified silicon rubber
Glue sealing element, wherein the condition vulcanized are as follows: 160 DEG C, 20MPa, 25sec.
Mesh size of crossing in the step 2 is 2-10 μm.
The methyl vinyl silicone rubber, reinforcing agent, activating agent, dispersing agent, anti-aging agent, vulcanizing agent, fatty alcohol polyoxy third
The mass ratio of alkene ether is 50-70:1-5:1-5:5-10:1-5:1-5:5-10.
The reinforcing agent the preparation method comprises the following steps: soft graphite is add to deionized water, be heated to reflux state, keep the temperature
5-10min is stirred, 2,5-dihydroxybenzoic acid then is added and tetraethyl titanate, return stirring 0.5-2h are subsequently added into nanometer
Aluminium oxide and silicon carbide, 80-90 DEG C of stirring 30-50min, are filtered, gained precipitating is washed away with deionized water and dehydrated alcohol while hot
Impurity is sent into 100-110 DEG C of drying box, is dried to constant weight to get reinforcing agent is arrived.
The soft graphite, 2,5- dihydroxy-benzoic acid, tetraethyl titanate, nano aluminium oxide, silicon carbide mass ratio be
20-30:20-25:1-2:10-15:5-10.
The activating agent is selected from zinc oxide or stearic acid.
The dispersing agent is polyethylene glycol 400.
The anti-aging agent is selected from ketone amines antioxidants or diphenylamine anti-aging agent.
The vulcanizing agent is benzoyl peroxide.
Soft graphite be by natural graphite scale through intercalation, washing, drying, high temperature puffing obtain one kind it is loose porous
Vermiform substance also has day other than having the excellent performances such as the cold-hot of natural graphite itself, corrosion-resistant, self-lubricating
The spies such as the unexistent softness of right graphite, compression resilience, adsorptivity, ecological environment harmony, biocompatibility, radiation resistance
Property.
The crystal form of nano aluminium oxide is γ-Al2O3, even particle size distribution, purity is high, the strengthening and toughening as silicon rubber,
It can be improved compactness, finish, cool-hot fatigue, the fracture toughness of silicon rubber.
Reaction principle according to the present invention is as follows:
(1) intermolecular esterification occurs for 2,5-dihydroxybenzoic acid, together under the action of catalyst tetraethyl titanate
When molecule in extra hydroxyl hydrogen bond action can occur link together, improve the stability of compound, what esterification generated
Substance is adsorbed in the lamella of soft graphite, improves soft graphite to the adsorptivity of inorganic material and to the affine of organic material
Property, while modified soft graphite has certain gain effect to the ageing resistance of silicon rubber；Nano aluminium oxide, silicon carbide can
To promote the hardness and wearability of silicon rubber, by the carrier function of soft graphite, can solve nano aluminium oxide, silicon carbide with
The problem of silicon rubber combination effect difference, gives full play to the function and effect of each component raw material；
(2) vulcanizing agent benzoyl peroxide is also the initiator of polymerization reaction simultaneously, is carried out in methyl vinyl silicone rubber
During vulcanization, with the unsaturated bond in silicon rubber part polyaddition reaction can occur for fatty alcohol polyoxypropylene ether, significantly
Improve the physical property of methyl vinyl silicone rubber.
The beneficial effects of the present invention are:
(1) present invention is modified processing to soft graphite, improves the ageing resistance of silicon rubber；It is modified soft simultaneously
Property graphite can solve that nano aluminium oxide, silicon carbide is ineffective in conjunction with silicon rubber, raw material effect is unable to give full play asks
Topic, improves stretching, the bending strength of silicon rubber；
(2) benzoyl peroxide is also the initiator of polymerization reaction simultaneously, is vulcanized in methyl vinyl silicone rubber
In the process, with the part unsaturated bond in silicon rubber polyaddition reaction can occur for fatty alcohol polyoxypropylene ether, be obviously improved
The physical properties such as tensile strength, the impact resistant strength of methyl vinyl silicone rubber；
(3) silicone-rubber seals prepared by the present invention, impact resistance, good seal performance, excellent physical properties, simple process are high
Effect is suitble to industrialized production.
Specific embodiment:
In order to be easy to understand the technical means, the creative features, the aims and the efficiencies achieved by the present invention, tie below
Specific embodiment is closed, the present invention is further explained.
Embodiment 1
(1) 60kg methyl vinyl silicone rubber is put into mixer the 10min that plasticates；
(2) methyl vinyl silicone rubber after plasticating, 2kg reinforcing agent, 2kg activating agent, 6kg dispersing agent and 2kg is anti-old
Agent is added in two-roll mill, is heated with stirring to 350 DEG C, mixing speed 800r/min, reacts 30min, slow cooling to 80
DEG C, mixture sieving sorting obtains sieving product；
(3) the sieving product of step 2 is injected in seal mold appropriate, 2kg vulcanizing agent and 6kg poly alkyl alcohol is added
Oxypropylene ether, suppresses sealing element type embryo, and sealing element type embryo is immersed in the mixed liquor of 4,4'- dichloro diphenyl sulfone and tetraethyl orthosilicate
Carry out curing reaction, reaction time 1h；
(4) the sealing element curing type embryo of step 3 is put into high pressure-temperature sintering furnace and carries out pressurized, heated molding and vulcanization,
Reacting furnace temperature be 200 DEG C, pressure 80MPa, slowly pressurize, keep high pressure-temperature reaction 20min after, carry out Temperature fall and
Decompression is until consistent with external environment；
(5) sealing element molding in step 4 is put into inert gas reacting furnace and is heated to 65 DEG C, soaking time 15min,
The disodium bicarbonate solution for being 7.5% to sealing element sprinkling mass fraction, carries out stripper member process, obtains product among sealing element；
(6) product among the sealing element of step 5 are placed on vulcanizing press, are further vulcanized, obtains modified silicon rubber
Glue sealing element, wherein the condition vulcanized are as follows: 160 DEG C, 20MPa, 25sec.
The preparation of reinforcing agent: 2kg soft graphite is add to deionized water, and is heated to reflux state, insulated and stirred
5min, is then added 2kg2,5- dihydroxy-benzoic acid and 0.1kg tetraethyl titanate, and return stirring 1h is subsequently added into 1kg nanometers
Aluminium oxide and 0.8kg silicon carbide, 80 DEG C of stirring 30min, are filtered while hot, and gained precipitating deionized water and dehydrated alcohol wash away miscellaneous
Matter is sent into 100-110 DEG C of drying box, is dried to constant weight to get reinforcing agent is arrived.
Embodiment 2
(1) 60kg methyl vinyl silicone rubber is put into mixer the 10min that plasticates；
(2) methyl vinyl silicone rubber after plasticating, 2kg reinforcing agent, 2kg activating agent, 6kg dispersing agent and 2kg is anti-old
Agent is added in two-roll mill, is heated with stirring to 350 DEG C, mixing speed 800r/min, reacts 30min, slow cooling to 80
DEG C, mixture sieving sorting obtains sieving product；
(3) the sieving product of step 2 is injected in seal mold appropriate, 2kg vulcanizing agent and 6kg poly alkyl alcohol is added
Oxypropylene ether, suppresses sealing element type embryo, and sealing element type embryo is immersed in the mixed liquor of 4,4'- dichloro diphenyl sulfone and tetraethyl orthosilicate
Carry out curing reaction, reaction time 1h；
(4) the sealing element curing type embryo of step 3 is put into high pressure-temperature sintering furnace and carries out pressurized, heated molding and vulcanization,
Reacting furnace temperature be 200 DEG C, pressure 80MPa, slowly pressurize, keep high pressure-temperature reaction 20min after, carry out Temperature fall and
Decompression is until consistent with external environment；
(5) sealing element molding in step 4 is put into inert gas reacting furnace and is heated to 65 DEG C, soaking time 15min,
The disodium bicarbonate solution for being 7.5% to sealing element sprinkling mass fraction, carries out stripper member process, obtains product among sealing element；
(6) product among the sealing element of step 5 are placed on vulcanizing press, are further vulcanized, obtains modified silicon rubber
Glue sealing element, wherein the condition vulcanized are as follows: 160 DEG C, 20MPa, 25sec.
The preparation of reinforcing agent: 2kg soft graphite is add to deionized water, and is heated to reflux state, insulated and stirred
5min, is then added 2kg2,5- dihydroxy-benzoic acid and 0.1kg tetraethyl titanate, and return stirring 1h is subsequently added into 1kg nanometers
Aluminium oxide and 0.8kg silicon carbide, 80 DEG C of stirring 30min, are filtered while hot, and gained precipitating deionized water and dehydrated alcohol wash away miscellaneous
Matter is sent into 100-110 DEG C of drying box, is dried to constant weight to get reinforcing agent is arrived.
Reference examples 1
(1) 60kg methyl vinyl silicone rubber is put into mixer the 10min that plasticates；
(2) methyl vinyl silicone rubber after plasticating, 2kg reinforcing agent, 2kg activating agent, 6kg dispersing agent and 2kg is anti-old
Agent is added in two-roll mill, is heated with stirring to 350 DEG C, mixing speed 800r/min, reacts 30min, slow cooling to 80
DEG C, mixture sieving sorting obtains sieving product；
(3) the sieving product of step 2 is injected in seal mold appropriate, 2kg vulcanizing agent and 6kg poly alkyl alcohol is added
Oxypropylene ether, suppresses sealing element type embryo, and sealing element type embryo is immersed in the mixed liquor of 4,4'- dichloro diphenyl sulfone and tetraethyl orthosilicate
Carry out curing reaction, reaction time 1h；
(4) the sealing element curing type embryo of step 3 is put into high pressure-temperature sintering furnace and carries out pressurized, heated molding and vulcanization,
Reacting furnace temperature be 200 DEG C, pressure 80MPa, slowly pressurize, keep high pressure-temperature reaction 20min after, carry out Temperature fall and
Decompression is until consistent with external environment；
(5) sealing element molding in step 4 is put into inert gas reacting furnace and is heated to 65 DEG C, soaking time 15min,
The disodium bicarbonate solution for being 7.5% to sealing element sprinkling mass fraction, carries out stripper member process, obtains product among sealing element；
(6) product among the sealing element of step 5 are placed on vulcanizing press, are further vulcanized, obtains modified silicon rubber
Glue sealing element, wherein the condition vulcanized are as follows: 160 DEG C, 20MPa, 25sec.
The preparation of reinforcing agent: 2kg soft graphite is add to deionized water, and is heated to reflux state, insulated and stirred
Then 0.1kg tetraethyl titanate is added in 5min, return stirring 1h is subsequently added into 1kg nano aluminium oxide and 0.8kg silicon carbide, and 80
DEG C stirring 30min, is filtered, gained precipitating deionized water and dehydrated alcohol wash away impurity, are sent into 100-110 DEG C of drying box while hot
In, it dries to constant weight to get reinforcing agent is arrived.
Reference examples 2
(1) 60kg methyl vinyl silicone rubber is put into mixer the 10min that plasticates；
(2) methyl vinyl silicone rubber after plasticating, 2kg reinforcing agent, 2kg activating agent, 6kg dispersing agent and 2kg is anti-old
Agent is added in two-roll mill, is heated with stirring to 350 DEG C, mixing speed 800r/min, reacts 30min, slow cooling to 80
DEG C, mixture sieving sorting obtains sieving product；
(3) the sieving product of step 2 is injected in seal mold appropriate, 2kg vulcanizing agent and 6kg poly alkyl alcohol is added
Oxypropylene ether, suppresses sealing element type embryo, and sealing element type embryo is immersed in the mixed liquor of 4,4'- dichloro diphenyl sulfone and tetraethyl orthosilicate
Carry out curing reaction, reaction time 1h；
(4) the sealing element curing type embryo of step 3 is put into high pressure-temperature sintering furnace and carries out pressurized, heated molding and vulcanization,
Reacting furnace temperature be 200 DEG C, pressure 80MPa, slowly pressurize, keep high pressure-temperature reaction 20min after, carry out Temperature fall and
Decompression is until consistent with external environment；
(5) sealing element molding in step 4 is put into inert gas reacting furnace and is heated to 65 DEG C, soaking time 15min,
The disodium bicarbonate solution for being 7.5% to sealing element sprinkling mass fraction, carries out stripper member process, obtains product among sealing element；
(6) product among the sealing element of step 5 are placed on vulcanizing press, are further vulcanized, obtains modified silicon rubber
Glue sealing element, wherein the condition vulcanized are as follows: 160 DEG C, 20MPa, 25sec.
Reinforcing agent: nano aluminium oxide and silicon carbide, mass ratio 10-15:5-10.
Reference examples 3
(1) 60kg methyl vinyl silicone rubber is put into mixer the 10min that plasticates；
(2) methyl vinyl silicone rubber after plasticating, 2kg reinforcing agent, 2kg activating agent, 6kg dispersing agent and 2kg is anti-old
Agent is added in two-roll mill, is heated with stirring to 350 DEG C, mixing speed 800r/min, reacts 30min, slow cooling to 80
DEG C, mixture sieving sorting obtains sieving product；
(3) the sieving product of step 2 is injected in seal mold appropriate, 2kg vulcanizing agent is added, suppress sealing element type
Embryo, sealing element type embryo, which is immersed in the mixed liquor of 4,4'- dichloro diphenyl sulfone and tetraethyl orthosilicate, carries out curing reaction, the reaction time
For 1h；
(4) the sealing element curing type embryo of step 3 is put into high pressure-temperature sintering furnace and carries out pressurized, heated molding and vulcanization,
Reacting furnace temperature be 200 DEG C, pressure 80MPa, slowly pressurize, keep high pressure-temperature reaction 20min after, carry out Temperature fall and
Decompression is until consistent with external environment；
(5) sealing element molding in step 4 is put into inert gas reacting furnace and is heated to 65 DEG C, soaking time 15min,
The disodium bicarbonate solution for being 7.5% to sealing element sprinkling mass fraction, carries out stripper member process, obtains product among sealing element；
(6) product among the sealing element of step 5 are placed on vulcanizing press, are further vulcanized, obtains modified silicon rubber
Glue sealing element, wherein the condition vulcanized are as follows: 160 DEG C, 20MPa, 25sec.
The preparation of reinforcing agent: 2kg soft graphite is add to deionized water, and is heated to reflux state, insulated and stirred
5min, is then added 2kg2,5- dihydroxy-benzoic acid and 0.1kg tetraethyl titanate, and return stirring 1h is subsequently added into 1kg nanometers
Aluminium oxide and 0.8kg silicon carbide, 80 DEG C of stirring 30min, are filtered while hot, and gained precipitating deionized water and dehydrated alcohol wash away miscellaneous
Matter is sent into 100-110 DEG C of drying box, is dried to constant weight to get reinforcing agent is arrived.
Embodiment 3
Based on embodiment 1, setting does not add the reference examples 1 of 2,5-dihydroxybenzoic acid, with white carbon black and silicon carbide
For reinforcing agent reference examples 2, do not add the reference examples 3 of fatty alcohol polyoxypropylene ether.
Sealing element is prepared using embodiment 1-2, reference examples 1-3, and the performance of sealing element is measured, as a result such as table 1
It is shown.
The performance test of 1 sealing element of table
| Test item | Tensile strength (MPa) | Bending strength (MPa) | Impact strength (KJ/m2) |
| Embodiment 1 | 97 | 94 | 103 |
| Embodiment 2 | 98 | 95 | 104 |
| Reference examples 1 | 79 | 74 | 86 |
| Reference examples 2 | 67 | 63 | 74 |
| Reference examples 3 | 63 | 61 | 71 |
Test method: tensile strength ASTM D638；Bending strength ASTM D790；Impact strength ISO179-2000 (E).
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (4)
1. a kind of preparation method of modified silicon rubber sealing element, which comprises the following steps:
(1) methyl vinyl silicone rubber is put into mixer the 10-20min that plasticates；
(2) by the methyl vinyl silicone rubber after plasticating, reinforcing agent, activating agent, dispersing agent and anti-aging agent, two-roll mill is added
In, be heated with stirring to 350-360 DEG C, mixing speed 800-900r/min, react 30-50min, slow cooling to 80-90 DEG C,
Mixture sieving sorting, obtains sieving product；
(3) the sieving product of step 2 is injected in seal mold appropriate, vulcanizing agent and fatty alcohol polyoxypropylene ether is added,
Sealing element type embryo is suppressed, sealing element type embryo, which is immersed in the mixed liquor of 4,4'- dichloro diphenyl sulfone and tetraethyl orthosilicate, to be solidified
Reaction, reaction time 1-2h；
(4) the sealing element curing type embryo of step 3 is put into high pressure-temperature sintering furnace and carries out pressurized, heated molding and vulcanization, reaction
Furnace temperature is 200-300 DEG C, pressure 80-90MPa, is slowly pressurizeed, and after keeping high pressure-temperature reaction 20-40min, carries out nature
Cooling and decompression are until consistent with external environment；
(5) sealing element molding in step 4 is put into inert gas reacting furnace and is heated to 65-70 DEG C, soaking time 15-
20min, the disodium bicarbonate solution for being 7.5% to sealing element sprinkling mass fraction, carries out stripper member process, obtains in sealing element
Between product；
(6) product among the sealing element of step 5 are placed on vulcanizing press, are further vulcanized, it is close obtains modified silicon rubber
Sealing, wherein the condition vulcanized are as follows: 160 DEG C, 20MPa, 25sec.
2. the preparation method of modified silicon rubber sealing element according to claim 1, it is characterised in that: in the step 2
Crossing mesh size is 2-10 μm.
3. the preparation method of modified silicon rubber sealing element according to claim 1, it is characterised in that: the activating agent is selected from
Zinc oxide or stearic acid；The dispersing agent is polyethylene glycol 400；The anti-aging agent is selected from ketone amines antioxidants or diphenylamine is anti-
Old agent；The vulcanizing agent is benzoyl peroxide.
4. the preparation method of modified silicon rubber sealing element according to claim 1, it is characterised in that: the methyl ethylene
Silicon rubber, reinforcing agent, activating agent, dispersing agent, anti-aging agent, vulcanizing agent, fatty alcohol polyoxypropylene ether mass ratio be 50-70:1-
5:1-5:5-10:1-5:1-5:5-10.
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| CN115286920A (en) * | 2022-09-16 | 2022-11-04 | 扬州塔川机械设备制造有限公司 | Sealing element material for high-pressure-resistant machinery and preparation method thereof |
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| CN111892712A (en) * | 2020-07-24 | 2020-11-06 | 天鼎联创密封技术（北京）有限公司 | Flexible graphite-silicon nitrogen polymer elastic material and preparation method thereof |
| CN111961945A (en) * | 2020-07-25 | 2020-11-20 | 安徽龙行密封件有限公司 | Friction block containing manganese-based complex powder and preparation method thereof |
| CN115286920A (en) * | 2022-09-16 | 2022-11-04 | 扬州塔川机械设备制造有限公司 | Sealing element material for high-pressure-resistant machinery and preparation method thereof |
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