CN101612824B - Metal/ceramic three-layer composite material, preparation process and application thereof - Google Patents
Metal/ceramic three-layer composite material, preparation process and application thereof Download PDFInfo
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- CN101612824B CN101612824B CN2009103052026A CN200910305202A CN101612824B CN 101612824 B CN101612824 B CN 101612824B CN 2009103052026 A CN2009103052026 A CN 2009103052026A CN 200910305202 A CN200910305202 A CN 200910305202A CN 101612824 B CN101612824 B CN 101612824B
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Abstract
The invention discloses a metal/ceramic three-layer composite material, a preparation process and application thereof. The metal/ceramic three-layer composite material consists of a metal layer, a ceramic layer and a metal/ceramic transition layer, wherein the metal/ceramic transition layer is positioned between the metal layer and the ceramic layer, the thickness of the metal/ceramic transition layer accounts for 50 to 75 percent of the total thickness of the composite material, and the thicknesses of the metal layer and that of the ceramic layer are equal. The invention also comprises the preparation process for the metal/ceramic three-layer composite material. The metal/ceramic three-layer composite material has the advantages of good abrasion resistance, high temperature resistance and corrosion resistance; and a hydraulic cylinder which is assembled with a cylinder barrel made of the composite material has stable and reliable work, long service life and low maintenance cost.
Description
Technical field
The present invention relates to a kind of metal/ceramic composite and preparation technology thereof and application, especially relate to a kind of metal/ceramic 3-layer composite material and preparation technology and application.
Background technology
The unification of multinomial performances such as the wearability of material and toughness is one of focus of modern material research.
Pottery is a kind of high performance material that integrates wear-resisting, high temperature resistant, high rigidity and multiple premium properties such as anticorrosive, but at normal temperatures, poor toughness, and difficult forming; Metal is then on the contrary, has ceramic unexistent plasticity and toughness, and these two kinds of materials are combined with each other through certain process, constitutes a kind of new construction material, should have both both advantages.
Hydraulic cylinder daily life with produce in application more and more widely, the main problem that exists is that hydraulic cylinder inwall and wearing for piston are serious day by day, cause oil cylinder because of scratch leakage of oil, pressure release along with hydraulic cylinder increases service time.In order to solve the wear-resisting problem of hydraulic cylinder; The method that generally adopts at present is that the hydraulic cylinder inwall is carried out roll extrusion, grinding, high-frequency quenching, chromium plating, laser treatment or the like; These technology costs are higher relatively; And the wearability lifting to hydraulic cylinder is also little, uses after about 2 years still heavy wear can occur, even scraps.
Summary of the invention
The objective of the invention is in order to overcome the above-mentioned defective that prior art exists; Provide a kind of wear-resisting, high temperature resistant, corrosion-resistant and have the metal/ceramic 3-layer composite material and a preparation technology thereof of plasticity and toughness; Use the hydraulic cylinder of this metal/ceramic 3-layer composite material manufacturing can prevent effectively that the long-term friction of piston from causing the scratch and the pressure release of hydraulic cylinder inwall, prolong service life.
The objective of the invention is to realize through following technical scheme:
The present invention's metal/ceramic 3-layer composite material, it is by metal level, ceramic layer; The metal/ceramic transition zone constitutes; The metal/ceramic transition zone is between metal level and ceramic layer, and said metal/ceramic transition region thickness accounts for the 50-75% of material gross thickness, and metal layer thickness equates with ceramic layer thickness.
Said metal level is mixed sintering and is formed by parent metal powder adding additive paraffin, formaldehyde, soybean oil, and each composition weight proportioning of said additive is: paraffin 47-55%, formaldehyde 43-52%, soybean oil 1.5-4.5%; Ceramic layer is formed by matrix ceramic powders adding additive paraffin, high density polyethylene (HDPE), stearic acid mixture sintering, and each composition weight proportioning of said additive is: paraffin 27-46%, high density polyethylene (HDPE) 35-45%, stearic acid 15-30%; The metal/ceramic transition zone is formed by the mixture sintering of parent metal powder and matrix ceramic powders and additive; And the metal dust kind is identical with the parent metal powder of metal level; Ceramic powders is identical with the matrix ceramic powders kind of ceramic layer; Metal dust accounts for the 8%-12% of whole powder qualities, and additive component and weight proportion do; High density polyethylene (HDPE) 30-45%, stearic acid 6-11%, paraffin 25-35%, Tissuemat E 8-15%, polypropylene 8-15%; The weight proportion of said various powder and additive is: powder 65-75% (preferred 70%), additive 25-35% (preferred 30%).
Said metal dust can be iron-zinc alloy powder, alumin(i)um zinc alloy powder or peptide-nickel alloy powder;
Said ceramic powders can be Si
3N
4Ceramic powders, SiC ceramic powders, Al
2O
3Ceramic powders, AlN ceramic powders or TiB
2Ceramic powders.
The preparation technology of metal/ceramic 3-layer composite material of the present invention is:
1) three kinds of different powder stocks are ground thinning processing respectively, particle diameter is controlled in the 0.8 μ m-1.2 mu m range, and mixes with respective additive;
2) with three kinds of different compounds extruding pelletization in double screw extruder respectively, particle diameter finally is controlled at 3mm-5mm;
3) said three kinds of different compounds are processed base substrate through the layering injection molding technique;
4) with base substrate at 280-320 ℃, under two atmospheric nitrogen atmospheres degreasing 46-55 hour, under 1500-1600 ℃, 200-260Mpa, formed fine and close workpiece again in sintering 50-70 minute.
Pottery and metal powder cognition generation reaction in-situ forms pottery and composite metal in sintering process, and the various additives that add in the powder help the combination at pottery and metal interface place.The physicochemical property of metal/ceramic transition zone is between metal level and ceramic layer; On the one hand relaxed the conflict between two kinds of different materials different performances; Mode through physics infiltration and chemical reaction can well combine metal level and ceramic layer on the other hand; Promote power and hot transmission between two kinds of different materials, effectively improve the composite performance of material.The modulus of pottery is much larger than metal; The toughness of metal is superior to pottery; Not only contain metal ingredient but also contain ceramic component in the ceramic/metal transition zone, weakened the sudden change on metal level and the ceramic layer structure, weakened overall modulus and the metal level of ceramic/metal transition zone, the gap between the ceramic layer; Reduce the residual stress that metal level, ceramic layer structure produce under external force, improved the anti-vibration performance of material.
Metal/ceramic 3-layer composite material anti-wear performance of the present invention is good, high temperature resistant, corrosion-resistant, be equipped with the hydraulic cylinder works of the cylinder barrel of its manufacturing reliable and stable, long service life, maintenance cost is low, has expanded range of application.
Description of drawings
Fig. 1 is a metal/ceramic 3-layer composite material structural representation of the present invention.
Fig. 2 is for using the hydraulic cylinder structure sketch map of metal/ceramic 3-layer composite material.
The specific embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is described further.
Embodiment 1
With reference to Fig. 1, the metal/ceramic 3-layer composite material embodiment of present embodiment is by fe-zn alloy layer 1, Si
3N
4 Ceramic layer 3, iron-zinc alloy/Si
3N
4Pottery transition zone 2 constitutes, fe-zn alloy layer 1 thick 3 millimeters, Si
3N ceramic layer 3 thick 3 millimeters, iron-zinc alloy/Si
3N
4Pottery transition zone 2 thick 8 millimeters.
Said fe-zn alloy layer 1 is mixed sintering and is formed by iron matrix Zinc alloy powder adding additive paraffin, formaldehyde, soybean oil, and weight proportion is: iron-zinc alloy powder: paraffin: formaldehyde: soybean oil=0.7: 0.12: 0.13: 0.05; Si
3N
4 Ceramic layer 3 is by Si
3N
4Ceramic powders and additive paraffin, polyethylene, stearic acid mix sintering and form, and weight proportion is: Si
3N
4Ceramic powders: paraffin: polyethylene: stearic acid=0.7: 0.11: 0.1: 0.09; Iron-zinc alloy/Si
3N
4Pottery transition zone 2 is by iron matrix Zinc alloy powder and Si
3N
4Ceramic powders and additive mix sintering and form, and all powder and additive mass ratio are: 7: 3, and the iron-zinc alloy content of powder accounts for 10% of whole powder weight, Si
3N
4Ceramic powders accounts for 90% of whole powder weight, and weight of additive consists of: high density polyethylene (HDPE) high density polyethylene (HDPE) 42%, stearic acid 10%, paraffin 26%, Tissuemat E 12%, polypropylene 10%.
The preparation technology of the metal/ceramic 3-layer composite material embodiment of present embodiment is: 1) each layer powder stock ground thinning processing respectively, particle diameter is controlled in the 0.8 μ m-1.2 mu m range, and mixes with said various additives; 2) with each layer compound extruding pelletization in double screw extruder respectively, particle diameter is controlled at 3mm-5mm; 3) said layers of material is processed hydraulic cylinder cylinder barrel base substrate through layering injection moulding; 4) with hydraulic cylinder cylinder barrel base substrate at 300 ℃, degreasing is 48 hours under two atmospheric nitrogen atmospheres, sintering formed fine and close hydraulic cylinder workpiece in 1 hour under 1550 ℃ of 250Mpa again.
Assembling (with reference to Fig. 2) with the hydraulic cylinder member: piston rod 6 is affixed through screw thread and piston 5, and centres, piston 5 surface are equipped with caulking gum packing ring 4, and piston rod 6 passes fairlead 7, the piston 5 said hydraulic cylinder cylinder barrel of packing into.
There are not seamless steel pipe inner surface convex helix in said composite ceramic layer 3 smooth surfaces and Never-rusty, and resistance coefficient is very little, and during piston 5 operations, the frictional force between piston 5 and the hydraulic cylinder inner surface reduces, and energy loss reduces thereupon.Under the normal temperature, when the hydraulic cylinder cylindrical shell was stressed, metal level 1 was different with ceramic layer 3 elastic modelling quantity; Ceramic layer 3 distortion are little, show as pressure, and metal level 1 distortion is big; Show as pulling force, when temperature raises, again because both coefficients of expansion are different; New stress field that thermal expansion produces and original stress field are cancelled out each other, and reach new balance, so can adapt to the different working temperatures condition.
Said internal layer ceramic layer 3 hardness are high; Heat-resisting, rub resistance, corrosion resistance are strong; In the course of work, even piston 5 can not cause scratch to the hydraulic cylinder inwall yet under very big uneven loading action, the corrosion component that contains in the hydraulic oil can not cause corrosion to the inner surface of hydraulic cylinder yet.Metal level 1 quality is softer, and very strong ductility and toughness are arranged, and when hydraulic cylinder received serious impact or static pressure, this structure can absorb impact energy effectively, reduces the damage to ceramic layer 3 of impact and too high static pressure.
The internal diameter 20mm hydraulic cylinder that uses the present embodiment composite to make through detecting and use test, does not have any damage at 900 ℃ of high temperature lower cylinder bodies; Inboard wall of cylinder block did not have any corrosion phenomenon in 72 hours at the concentrated sulfuric acid and concentrated hydrochloric acid effect; With the plunger pole supporting under 300Mpa pressure 500,000 inboard wall of cylinder block of continuous operation do not have any noticeable wear sign.
Embodiment 2
3 millimeters of the present invention's metal/ceramic 3-layer composite material embodiment alumin(i)um zinc alloy bed thickness, 3 millimeters of SiC pottery bed thickness, 6 millimeters of the ceramic transition bed thickness of alumin(i)um zinc alloy/SiC, alumin(i)um zinc alloy/SiC pottery transition zone is between alumin(i)um zinc alloy layer and SiC ceramic layer.
Said alumin(i)um zinc alloy layer is mixed sintering and is formed by base aluminum Zinc alloy powder and additive paraffin, formaldehyde, soybean oil; Weight proportion is: alumin(i)um zinc alloy powder: paraffin: formaldehyde: soybean oil=0.7: 0.12: 0.1: 0.08; The ceramic layer component is mixed sintering and is formed by SiC ceramic powders and additive paraffin, polyethylene, stearic acid, and its weight ratio is: SiC ceramic powders: paraffin: polyethylene: stearic acid=0.68: 0.09: 0.15: 0.08; Alumin(i)um zinc alloy/SiC pottery transition zone mixes sintering by base aluminum Zinc alloy powder, SiC ceramic powders and additive and forms, and the mass ratio of all powder raw material and additive is 0.7: 0.3, and the alumin(i)um zinc alloy powder accounts for 8% of whole powder stock quality; The SiC ceramic powders accounts for 92% of whole powder weight; Weight of additive consists of: high density polyethylene (HDPE) high density polyethylene (HDPE) 45%, stearic acid 7%, paraffin 30%; Tissuemat E 8%, polypropylene 10%.
Preparation technology is with embodiment 1.
The internal diameter 20mm hydraulic cylinder that uses the present embodiment composite to make through detecting and use test, does not have any damage at 800 ℃ of high temperature lower cylinder bodies; Inboard wall of cylinder block did not have any corrosion phenomenon in 72 hours at the concentrated sulfuric acid and concentrated hydrochloric acid effect; With the plunger pole supporting under 300Mpa pressure 500,000 inboard wall of cylinder block of continuous operation do not have any noticeable wear sign.
2.5 millimeters of the present invention's metal/ceramic 3-layer composite material embodiment metal bed thickness, 2.5 millimeters of ceramic bed thickness, 7 millimeters of metal/ceramic transition bed thickness, the metal/ceramic transition zone is between metal level and ceramic layer.
Said metal level is mixed sintering and is formed by matrix peptide-nickel alloy powder and additive paraffin, formaldehyde, soybean oil, and its weight ratio is: peptide-nickel alloy powder: paraffin: formaldehyde: soybean oil=0.65: 0.15: 0.12: 0.8, and the ceramic layer component is by Al
2O
3Ceramic powders and additive paraffin, polyethylene, stearic acid mix sintering and form, and its weight ratio is: Al
2O
3Ceramic powders: paraffin: polyethylene: stearic acid=0.65: 0.11: 0.14: 0.10; The metal/ceramic transition zone is by matrix peptide-nickel alloy powder, Al
2O
3Ceramic powders and additive mix sintering and form, and the mass ratio of all powder raw material and additive is 0.7: 0.3, and peptide-nickel alloy powder accounts for 9% of all material powder quality, Al
2O
3Ceramic powders accounts for 91% of whole powder weight, and weight of additive consists of: high density polyethylene (HDPE) 40%, stearic acid 10%, paraffin 25%, Tissuemat E 10%, polypropylene 15%.
The preparation technology of the present invention's metal/ceramic 3-layer composite material embodiment is: 1) three layers of different powder stock are ground thinning processing respectively, particle diameter is controlled in the 0.8 μ m-1.2 mu m range, and mixes with above-mentioned various additives; 2) with three layers of different powder mixture extruding pelletization in double screw extruder respectively, particle diameter is controlled at 3mm-5mm; 3) said layers of material is processed hydraulic cylinder cylinder barrel base substrate through layering injection moulding; 4) with hydraulic cylinder cylinder barrel base substrate at 300 ℃, degreasing is 50 hours under two atmospheric nitrogen atmospheres, again at 1500 ℃, sintering formed fine and close hydraulic cylinder workpiece in 1 hour under the 200Mpa.
The internal diameter 20mm hydraulic cylinder that uses the present embodiment composite to make through detecting and use test, does not have any damage at 700 ℃ of high temperature lower cylinder bodies; Inboard wall of cylinder block did not have any corrosion phenomenon in 72 hours at the concentrated sulfuric acid and concentrated hydrochloric acid effect; With the plunger pole supporting under 300Mpa pressure 500,000 inboard wall of cylinder block of continuous operation do not have any noticeable wear sign.
2 millimeters of the present invention's metal/ceramic 3-layer composite material embodiment metal bed thickness, 2 millimeters of ceramic bed thickness, 8 millimeters of metal/ceramic transition bed thickness, the metal/ceramic transition zone is between metal level and ceramic layer.
Said metal level is mixed sintering and is formed by iron matrix Zinc alloy powder and additive paraffin, formaldehyde, soybean oil; Their weight ratio is: 0.67: 0.14: 0.14: 0.05; Ceramic layer is mixed sintering and is formed by AlN ceramic powders and additive paraffin, polyethylene, stearic acid; Its weight ratio is: the AlN ceramic powders: paraffin, polyethylene, stearic acid 0.67: 0.15: 0.13: 0.05, and the metal/ceramic transition zone mixes sintering by iron-zinc alloy powder, AlN ceramic powders and additive and forms, and the mass ratio of all powder raw material and additive is 0.7: 0.3; And Al alloy powder accounts for 11% of all material powder powder qualities, Al
2O
3Ceramic powders accounts for 89% of whole powder weight, and additive is a high density polyethylene (HDPE) 30%, stearic acid 10%, paraffin 30%, Tissuemat E 15%, polypropylene 15%.
Preparation technology and embodiment 1 are roughly the same.
The internal diameter 20mm hydraulic cylinder that uses the present embodiment composite to make through detecting and use test, does not have any damage at 700 ℃ of high temperature lower cylinder bodies; Inboard wall of cylinder block did not have any corrosion phenomenon in 48 hours under the concentrated sulfuric acid and concentrated hydrochloric acid effect; With the plunger pole supporting under 300Mpa pressure 500,000 inboard wall of cylinder block of continuous operation do not have any noticeable wear sign.
Embodiment 5
1.5 millimeters of the present invention's metal/ceramic 3-layer composite material embodiment metal bed thickness, 1.5 millimeters of ceramic bed thickness, 9 millimeters of metal/ceramic transition bed thickness, the metal/ceramic transition zone is between metal level and ceramic layer.
Said metal level component comprises that iron matrix Zinc alloy powder and additive paraffin, formaldehyde, soybean oil mix sintering and form, and its weight ratio is: 0.70: 0.12: 0.11: 0.07, and the ceramic layer component comprises TiB
2Ceramic powders and additive paraffin, polyethylene, stearic acid mix sintering and form, and its weight ratio is: 0.70: 0.10: 0.13: 0.07, and metal/ceramic transition zone component comprises that the iron matrix Zinc alloy powder mixes sintering and forms; The mass ratio of all powder raw material and additive is 0.7: 0.3; And the iron-zinc alloy powder accounts for 12% of whole material powder powder qualities, and TiB porcelain powder accounts for 88% of whole powder weight, and weight of additive consists of high density polyethylene (HDPE) 43%; Stearic acid 11%; Paraffin 30%, Tissuemat E 8%, polypropylene 8%.
The preparation technology of the present invention's metal/ceramic 3-layer composite material embodiment is: 1) three layers of different powder stock are ground thinning processing respectively, particle diameter is controlled in the 0.8 μ m-1.2 mu m range, and mixes with above-mentioned various additives; 2) with three layers of different powder mixture extruding pelletization in double screw extruder respectively, particle diameter finally is controlled at 3mm-5mm; 3) said layers of material is processed hydraulic cylinder cylinder barrel base substrate through layering injection moulding; 4) with hydraulic cylinder cylinder barrel base substrate at 290 ℃, degreasing is 55 hours under two atmospheric nitrogen atmospheres, sintering formed fine and close hydraulic cylinder workpiece in 1 hour under 1550 ℃ of 210Mpa again.
The internal diameter 20mm hydraulic cylinder that uses the present embodiment composite to make through detecting and use test, does not have any damage at 700 ℃ of high temperature lower cylinder bodies; Inboard wall of cylinder block did not have any corrosion phenomenon in 24 hours under the concentrated sulfuric acid and concentrated hydrochloric acid effect; With the plunger pole supporting under 300Mpa pressure 500,000 inboard wall of cylinder block of continuous operation do not have any noticeable wear sign.
Claims (3)
1. a metal/ceramic 3-layer composite material is characterized in that, by fe-zn alloy layer, Si
3N
4Ceramic layer, iron-zinc alloy/Si
3N
4The pottery transition zone constitutes 3 millimeters of iron-zinc alloy bed thickness, Si
3N
43 millimeters of pottery bed thickness, iron-zinc alloy/Si
3N
48 millimeters of pottery transition bed thickness;
Said fe-zn alloy layer is mixed sintering and is formed by iron matrix Zinc alloy powder adding additive paraffin, formaldehyde, soybean oil, and weight proportion is: iron-zinc alloy powder: paraffin: formaldehyde: soybean oil=0.7:0.12:0.13:0.05; Si
3N
4Ceramic layer is by Si
3N
4Ceramic powders and additive paraffin, polyethylene, stearic acid mix sintering and form, and weight proportion is: Si
3N
4Ceramic powders: paraffin: polyethylene: stearic acid=0.7:0.11:0.1:0.09; Iron-zinc alloy/Si
3N
4The pottery transition zone is by iron matrix Zinc alloy powder and Si
3N
4Ceramic powders and additive mix sintering and form, and all powder and additive mass ratio are: 7:3, and the iron-zinc alloy content of powder accounts for 10% of whole powder weight, Si
3N
4Ceramic powders accounts for 90% of whole powder weight, and weight of additive consists of: high density polyethylene (HDPE) 42%, stearic acid 10%, paraffin 26%, Tissuemat E 12%, polypropylene 10%.
2. metal/ceramic 3-layer composite material; It is characterized in that; Constitute 3 millimeters of alumin(i)um zinc alloy bed thickness, 3 millimeters of SiC pottery bed thickness by alumin(i)um zinc alloy layer, SiC ceramic layer, alumin(i)um zinc alloy layer/SiC pottery transition zone; 6 millimeters of the ceramic transition bed thickness of alumin(i)um zinc alloy/SiC, alumin(i)um zinc alloy/SiC pottery transition zone is between alumin(i)um zinc alloy layer and SiC ceramic layer;
Said alumin(i)um zinc alloy layer is mixed sintering and is formed by base aluminum Zinc alloy powder and additive paraffin, formaldehyde, soybean oil; Weight proportion is: alumin(i)um zinc alloy powder: paraffin: formaldehyde: soybean oil=0.7:0.12:0.1:0.08; The ceramic layer component is mixed sintering and is formed by SiC ceramic powders and additive paraffin, polyethylene, stearic acid, and its weight ratio is: SiC ceramic powders: paraffin: polyethylene: stearic acid=0.68:0.09:0.15:0.08; Alumin(i)um zinc alloy/SiC pottery transition zone mixes sintering by base aluminum Zinc alloy powder, SiC ceramic powders and additive and forms, and the mass ratio of all powder raw material and additive is 0.7:0.3, and the alumin(i)um zinc alloy powder accounts for 8% of whole powder stock quality; The SiC ceramic powders accounts for 92% of whole powder weight; Weight of additive consists of: high density polyethylene (HDPE) 45%, stearic acid 7%, paraffin 30%; Tissuemat E 8%, polypropylene 10%.
3. the application of metal/ceramic 3-layer composite material in making the hydraulic cylinder cylinder barrel according to claim 1 or claim 2.
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| CN108672685A (en) * | 2018-05-21 | 2018-10-19 | 邱洪 | The three-layer composite pipe that ceramic tube is directly cast with metal |
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