CN102865220A - Engine fuel pump plunger with carbon nitride-based nano composite coating and manufacturing method thereof - Google Patents
Engine fuel pump plunger with carbon nitride-based nano composite coating and manufacturing method thereof Download PDFInfo
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Abstract
The invention discloses an engine fuel pump plunger with a carbon nitride-based nano composite coating and a manufacturing method of the engine fuel pump plunger with the carbon-nitride-based nano composite coating. A nano composite coating sequentially consisting of Cr, Cr/CrN, Ti, TiNx, TiN-CN and CN-TiN is generated on a diesel engine fuel pump plunger by an arc discharge method. According to the engine fuel pump plunger with the carbon-nitride-based nano composite coating and the manufacturing method of the engine fuel pump plunger with the carbon-nitride-based nano composite coating, the structural design of the coating is rational, and the prepared carbon-nitride-based nano composite coating has high capability of bonding with the base of the diesel engine fuel pump plunger, very high hardness (35 GPa) and good wear-resisting and lubricating properties, wherein the friction coefficient is less than 0.15; and the problem of sealing leakage caused by attrition between the fuel pump plunger and a pump body when the fuel pump plunger runs under a high pressure at a high speed is better overcome, and the service life and the lubricating property of the fuel pump plunger can be improved greatly, so that the carbon-nitride-based nano composite coating engine fuel pump plunger has a good industrial application foreground.
Description
Technical field
The present invention relates to the thin-film material technical field, particularly a kind of nitrogenize carbon back nano-composite coating diesel engine fuel-firing pump plunger and preparation method thereof.
Background technique
The advantage of diesel engine is that power is large, economic performance good.Usually, diesel engine is compared the thermal efficiency with petrol engine high by 30%, thereby on energy saving, cut the cost of fuel angle, promoting the use of of diesel engine is significant.Diesel engine compares with petrol engine that to have power large, life-span is long, the characteristics that power performance is good, and the greenhouse effect that its discharging produces are than gasoline low 45%, carbon monoxide and hydrocarbon emission are also low, the useful life period of car load oxynitride discharge be slightly larger than petrol engine.Reached at present Europe V standard abroad, and the discharging of China's diesel-engined vehicle is paced up and down about the III of Europe always, along with the strict demand of environmental protection and energy-conservation sustainable development, diesel-oil vehicle will be a main development trend.
Fuel pump is one of fundamental composition of automobile fuel injection system.Effect is being transported in the high-pressure oil feed pipe after fuel oil sucking-off from fuel tank, the pressurization, for the firing chamber provides oil plant.The diesel engine fuel-firing pump is one of topmost factor that affects engine performance.Be mainly manifested in its combustion efficiency that affects motor and discharging.The raising of oil fuel pump performance has conclusive effect to the diesel engine performance.But because long-term technical monopoly and the blockade of external fuel pump giant enterprise, the fuel injection system that only reaches Europe III emission standard that China uses at present is whole dependence on import almost, IV above fuel pump in Europe blocks China, not only expensive, and seriously restricted the development of national auto industry.
Carbonitride (C-N) film has the characteristics of high hardness, low coefficient of friction and high thermal stability, is a kind of novel superhard material, and its theoretical hardness is expected to replacing diamond in some occasion near diamond.Although the C-N appearance time soon, application is in day by day expansion.It can be used as surface abrasion coating and the high temperature resistance high pressure zone of various industrial products and extraordinary parts, makes product durable in use, increases the service life.Because its thermal conductivity is good, can in making vlsi circuit, bring into play special role, promote the development of microelectronic technology and computer technology.C-N can also be used for developing various novel high thermal conductivity devices.The C-N method for manufacturing thin film is a lot of at present, and the preparation method is very large to composition, structure and the performance impact of film.Preparation method commonly used has oscillating wave compression, high pressure pyrolysis, Implantation, low energy ion radiation, ion beam depositing, reactive sputtering, chemical vapor deposition, laser ablation, pulse laser induced, electrochemical deposition and Arc Discharge.Carbon nitride coatings has been carried out large quantity research both at home and abroad at present, but because preparation method's defective does not obtain large-scale commercial Application always.
Summary of the invention
Purpose of the present invention is exactly the present situation for above-mentioned prior art, and a kind of nitrogenize carbon back nano-composite coating diesel engine fuel-firing pump plunger and preparation method thereof is provided.
The technological scheme of product of the present invention is: be that the surface of the diesel engine fuel-firing pump plunger of alloyed steel has the nitrogenize carbon back nano-composite coating that is made of successively binder course I, supporting layer, binder course II, graded bedding, transition layer, lubricating layer from inside to outside at matrix, wherein, binder course I is the Cr layer; Supporting layer is the Cr/CrN layer; Binder course II is the Ti layer; Graded bedding is TiNx, and wherein the scope of X is 0＜X≤1; Transition layer is the TiN-CN layer; Lubricating layer is CN-TiN nanometer crystal layer.
For further improving the cost performance of product of the present invention:
1) thickness of described composite coating is the 3-15 micron, and wherein joint thickness is between the 10-30 nanometer; Supporting layer thickness is between the 1-10 micron; Binder course II thickness is between the 20-80 nanometer; Graded bedding thickness is between the 100-500 nanometer; Transition layer is between the 0.4-3 micron; Lubricating layer is between the 1-5 micron;
2) supporting layer is chosen as the Cr/CrN laminated coating that Cr layer and CrN layer alternately consist of;
3) lubricating layer is chosen as the CN-TiN nanocrystalline composite coating that the TiN Nanocrystals Embedded consists of in amorphous CN: the nanocrystalline diameter of its TiN is 3-50nm.
Preparation method's of the present invention technological scheme is: it is characterized in that being formed successively by following step:
1) to carrying out through the diesel engine fuel-firing pump plunger of chemical cleaning after aura cleans, at its surface deposition binder course I, this binder course I is the Cr layer;
2) the binder course I that obtained in the upper step deposits supporting layer, and this supporting layer is the Cr/CrN layer;
3) the supporting layer deposition binder course II that obtained in the upper step, this binder course II is the Ti layer;
4) the binder course II that obtained in the upper step deposits graded bedding, and this graded bedding is TiNx, and wherein the scope of X is 0＜X≤1;
5) graded bedding that obtained in the upper step deposits transition layer, and this transition layer is the TiN-CN layer;
6) transition layer that obtained in the upper step deposits lubricating layer, and this lubricating layer is CN-TiN nanometer crystal layer, naturally cooling, and get final product.
As preference:
Supporting layer is chosen as the Cr layer and the CrN layer replaces the Cr/CrN laminated coating that consists of:
Lubricating layer is chosen as the CN-TiN nanocrystalline composite coating that the TiN Nanocrystals Embedded consists of in amorphous CN.
Be further to improve work efficiency and the quality of the inventive method, can be further the actual conditions of each step be chosen in:
1) condition of described aura cleaning is: temperature is 150-500 ℃, under the ar gas environment;
2) sedimentary condition of described binder course I is: air pressure 0.005-0.5Pa, and voltage-700V arrives-1200V;
3) sedimentary condition of described supporting layer is: air pressure 0.3-0.5Pa, and voltage-50V arrives-250V;
4) sedimentary condition of described binder course II is: air pressure 0.005-0.5Pa, and voltage-600V is to 1200V;
5) sedimentary condition of described graded bedding is: progressively pass into nitrogen, nitrogen flow progressively increases, and range of flow is at 50-300sccm, and air pressure 0.1-2Pa, range of flow are at 50-300sccm, and bias voltage is 50-300V;
6) sedimentary condition of described transition layer is: progressively pass into acetylene, the acetylene flow progressively increases, at 50-300sccm; Nitrogen flow gradually reduces simultaneously, progressively is reduced to 100sccm from 300sccm; Bias voltage 50-200V;
7) sedimentary condition of described lubricating layer is: bias voltage-50V arrives-250V, air pressure 0.1-2Pa.
The present invention utilizes hollow cathode Arc Discharge carbon source and arc discharge method to prepare superhard carbonitride base composite coating as shown from the above technical solution.In order to improve the combination force between the coatings and substrate, the method at first utilizes the high ionization level of circular arc source that the Cr ion is evaporated from the Cr target, add negative high voltage at workpiece, the Cr ion cleans workpiece surface under the bias voltage bombardment and generates the Cr binder course at workpiece.Preparation through binder course, the body material composition has become single Cr from complexity polynary, progressively pass on this basis nitrogen, generate CrN with the Cr reaction, CrN is ceramic phase, its thermal expansion coefficient is higher than Cr, comparatively approaching with steel for the original position preparation, is metallurgy combination each other between CrN and the Cr, CrN hardness is 20GPa, the hardness of steel base is 5-6Gpa, in order to improve matrix hardness and to reduce stress, if the thicker CrN coating of preparation, then coating easily comes off, and this patent adopts the Cr/CrN multi-layer film structure that Cr and CrN form for this reason.This structure not only makes coating can prepare thicker thickness, and owing to the adding of Cr, CrN can form less columnar crystal, has improved the consistency of coating simultaneously.After the preparation through the Cr/CrN multi-layer film structure, plunger matrix surface hardness has reached 20GPa, has simultaneously preferably combination force and supporting effect.In order to carry out the preparation of CN composite coating on Cr/CrN multi-layer film structure basis, the art of this patent adopts the Ti electric arc target at the pure Ti layer of Cr/CrN multi-layer film structure surface preparation, mainly is to reach a progressive formation on the composition.And then pass into nitrogen, and generating the TiNx graded bedding with the Ti reaction, passing into of nitrogen keeps flow progressively to increase, and avoids causing larger stress to cause demoulding.The Ti:N ratio constantly changes among this layer TiNx for this reason, reaches at last Ti:N=1:1, forms the TiN of stoicheiometry.After the TiNx preparation finishes, progressively pass into acetylene in the stove, preparation TiN-CN transition layer II.Acetylene is become carbon ion by the hollow cathode carbon source by ionization, generates CN with the nitrogen reaction.The flow of acetylene progressively increases, and the content of CN also progressively increases, and forms from pure TiN to containing CN TiN, at last to the gradual transition that contains TiN CN coating.After TiN-CN transition layer II preparation finishes.Keep acetylene and nitrogen flow constant, preparation CN-TiN lubricating layer.
Design of the present invention is: adopt hollow Arc Discharge carbon source to produce carbon ion, utilize Arc Discharge Ti target to produce transition metal nitride (TiN), utilize both in conjunction with preparation CN-TiN nano-composite coating.Wherein the utilization of hollow Arc Discharge carbon source mainly is to overcome the present conventional graphite carbon source of using can produce large particle injection and the low shortcoming of magnetron sputtering graphite carbon source ionization level when Arc Discharge.The Arc Discharge carbon source that present technique adopts is acetylene gas owing to what adopt, and the problem that does not exist graphite granule to pollute can obtain the highly carbon ion of ionization.Avoided simultaneously the low ionization level state of magnetron sputtering carbon source.The use of Arc Discharge source metal can well be mixed to the CN coating in addition.For this reason, one aspect of the present invention makes composite coating have very high surface hardness, add can decrease coating internal stress for the transition metal nitrogen carbide on the other hand, improve the adhesive strength of coating, can overcome the shortcomings such as the coating internal stress that conventional CN coat preparing technology causes is high, poor adhesive force.Because apparatus structure is reasonable, can realizes batch process to the component of different structure shape, thereby have the commercial application prospect.
Therefore the present invention has following advantage: first, preparing the carbonitride method with the graphite target Arc Discharge compares, the present invention adopts hollow cathode arc source ionization level high, adopt simultaneously acetylene as carbon source, overcome the filtration system of the complexity that large particle that the filtering graphite target produces adopts, significantly simplified equipment; The second, the present invention compares with the magnetron sputtering graphite target, and the Arc Discharge ionization level is high, causes the hardness of coating high, and combination force is good; The 3rd, because coating structure of the present invention is reasonable, until the top lubricating layer not only has the composition gradual change, structural adjustment is also arranged, but the stress of decrease coating can satisfy the operation of plunger long-term stability from the bottom binder course; The 4th, the present invention adopts hollow cathode electric arc close with existing coating apparatus, and coating apparatus is simple in structure simultaneously, is easy to control, and prospects for commercial application is good;
Adopt the prepared carbon nitride coatings diesel engine fuel-firing pump plunger of the present invention to have good wear-resisting and greasy property, guaranteed the plunger long-term stable operation, the plunger wear rate is significantly descended, has simultaneously good greasy property, quality of processing is stable, work efficiency improves, and has reduced the cost of production of producer.
In a word, the prepared carbon nitride coatings diesel engine fuel-firing of the present invention pump plunger has that hardness is high, friction factor is low, significantly plunger working life, reduces production costs, and is easy to realize industrial production, has a good application prospect.
Description of drawings
Fig. 1. be the hollow cathode arc discharge device schematic diagram that adopts among the present invention;
Fig. 2. be the nitrogenize carbon back nano-composite coating structural representation of the present invention's preparation;
Fig. 3 is the nitrogenize carbon back nano-composite coating surface scan electromicroscopic photograph that the present invention prepares; .
Fig. 4. be the nitrogenize carbon back nano-composite coating Cross Section Morphology figure of the present invention's preparation;
Among above-mentioned Fig. 1: 1. bleeding point; 2. furnace wall; 3. titanium electric arc target; 4. fire door; 5. hollow cathode Arc Discharge carbon source; 6. central heater; 7. chromium target; 8. work rest;
Among above-mentioned Fig. 2: 1. plunger matrix; 2. binder course I; 3. supporting layer; 4. binder course II; 5. graded bedding; 6. transition layer; 7. lubricating layer
Embodiment
Adopt the hollow cathode arc discharge device when preparing product of the present invention with method of the present invention.Accompanying drawing 1 is the structural representation of this device, and the vacuum chamber of device is surrounded by square furnace wall 2, and the vacuum chamber height is 0.4-1.0 rice, and the straight flange length of side is for being 300-1200mm.The vacuum chamber side is provided with fire door 4, to make things convenient for the loading and unloading of workpiece.Vacuum chamber is provided with vacuum orifice 1, vacuumizes unit and vacuumizes by 1 pair of vacuum chamber of vacuum orifice, vacuumizes the pattern that unit adopts molecular pump+mechanical pump, and limiting vacuum can reach 5 * 10
-4Pa.The center portion of vacuum chamber is heater 6, and hollow cathode Arc Discharge carbon source 5 is installed on the fire door, and metal titanium targets and chromium target are installed on the furnace wall of both sides.Sample is contained on the work rest 8, revolves round the sun and rotation at the stove middle part.This layout increases considerably vacuum chamber ionic medium bulk density, and workpiece is immersed in the plasma fully.Coating deposition rate, hardness, adhesion are greatly improved.Because target structure is optimized, Magnetic field distribution is more even, makes electric arc evenly burning on target surface, has improved the uniformity of coating.
Below in conjunction with specific embodiment technological scheme of the present invention is described further.This embodiment is not the restriction to its protection domain.
Embodiment 1: under 150 ℃ of ar gas environments, to carry out through the diesel engine fuel-firing pump plunger of chemical cleaning aura clean finish after, at 0.005Pa, adopt arc ion plating (aip) to deposit the transition metal Cr binder course I of 10 nanometer thickness under the-700V condition; At 0.3Pa, the Cr/CrN supporting layer of-50V condition deposit 1 micron thick; Then 0.005Pa, the transition metal Ti binder course II of-600V condition deposit 10 nanometer thickness.Under the 0.1Pa condition, progressively pass into nitrogen subsequently, nitrogen flow progressively increases, and flow control is at 50sccm, and bias voltage is 50V, the TiNx graded bedding of preparation 100nm; Progressively pass into subsequently acetylene, prepare 0.4 micron TiN-CN transition layer II, the acetylene flow progressively increases, and changes between 50-300sccm, and bias voltage control is at 50V, and nitrogen flow gradually reduces simultaneously, progressively is reduced to 100sccm from 300sccm; After transition layer II preparation finishes, at-50V bias voltage, under the 0.1Pa condition, deposit 1 micron CN-TiN lubricating layer, the nanocrystalline diameter of its TiN is 3-50nm; Coating hardness is controlled at 30-35GPa, and friction factor is lower than 0.05-0.15; Approximately 2.5 microns of total coating thicknesses.Naturally cooling obtained nitrogenize carbon back nano-composite coating diesel engine fuel-firing pump plunger after preparation finished.
Embodiment 2: under 350 ℃ of ar gas environments, to carry out through the diesel engine fuel-firing pump plunger of chemical cleaning aura clean finish after, at 0.1Pa, adopt arc ion plating (aip) to deposit the transition metal Cr binder course I of 20 nanometer thickness under the-800V condition; At 0.4Pa, the Cr/CrN supporting layer of-150V condition deposit 4 micron thick; Then 0.4Pa, the transition metal Ti binder course II of-800V condition deposit 20 nanometer thickness.Progressively pass into subsequently nitrogen, nitrogen flow progressively increases, and last flow control is at 300sccm, and bias voltage is 100V, the TiNx graded bedding of preparation 300nm; Progressively pass into subsequently acetylene, prepare 2 microns TiN-CN transition layer II, the acetylene flow progressively increases, and changes between 50-300sccm, and bias voltage control is at 100V, and nitrogen flow gradually reduces simultaneously, progressively is reduced to 100sccm from 300sccm; After transition layer II preparation finishes ,-150V, under the 0.5Pa condition, deposit 2 microns CN-TiN lubricating layers, the nanocrystalline diameter of its TiN is 3-50nm; Coating hardness is controlled at 30-35GPa, and friction factor is lower than 0.05-0.15, approximately 8 microns of total coating thicknesses.Naturally cooling obtained nitrogenize carbon back nano-composite coating diesel engine fuel-firing pump plunger after preparation finished.
Embodiment 3: under 500 ℃ of ar gas environments, to carry out through the diesel engine fuel-firing pump plunger of chemical cleaning aura clean finish after, at 0.5Pa ,-1200V condition adopts arc ion plating (aip) to deposit the transition metal Cr binder course I of 30 nanometer thickness; At 0.5Pa ,-250V condition deposits the Cr/CrN supporting layer of 7 micron thick; Then 0.5Pa ,-1200V condition deposits the transition metal Ti binder course II of 30 nanometer thickness.Under the 2Pa condition, progressively pass into nitrogen subsequently, nitrogen flow progressively increases, and range of flow is at 50-300sccm, and bias voltage is 300V, the TiNx graded bedding of preparation 500nm; Progressively pass into subsequently acetylene, prepare 3 microns TiN-CN transition layer II, the acetylene flow progressively increases, and changes between 50-300sccm, and bias voltage control is at 200V, and nitrogen flow gradually reduces simultaneously, progressively is reduced to 100sccm from 300sccm; After transition layer II preparation finishes ,-the 250V bias voltage, under the 2Pa condition, deposit 5 microns CN-TiN lubricating layers, the nanocrystalline diameter of its TiN is 3-50nm; Coating hardness is controlled at 30-35GPa, and friction factor is lower than 0.05-0.15, approximately 15 microns of total coating thicknesses.Naturally cooling obtained nitrogenize carbon back nano-composite coating diesel engine fuel-firing pump plunger after preparation finished.
Fig. 2. be the nitrogenize carbon back nano-composite coating structural representation of the present invention's preparation; Can find out that therefrom coating not only has the composition gradual change, the structure gradual change is also arranged.Structure is comparatively reasonable, and coating stress is less.
Fig. 3 is the nitrogenize carbon back nano-composite coating surface scan electromicroscopic photograph that the present invention prepares; Can find out that therefrom coating surface is even, defective is less.
Fig. 4. be the nitrogenize carbon back nano-composite coating Cross Section Morphology figure of the present invention's preparation; Therefrom can find out coatings and substrate in conjunction with good, without obvious layering and defect situation.
Claims (8)
1. nitrogenize carbon back nano-composite coating diesel engine fuel-firing pump plunger is characterized in that:
The matrix of described diesel engine fuel-firing pump plunger is alloyed steel, and there is the nitrogenize carbon back nano-composite coating that is made of successively binder course I, supporting layer, binder course II, graded bedding, transition layer, lubricating layer from inside to outside on its surface, and:
1) binder course I is the Cr layer;
2) supporting layer is the Cr/CrN layer;
3) binder course II is the Ti layer;
4) graded bedding is TiNx, and wherein the scope of X is 0＜X≤1;
5) transition layer is the TiN-CN layer;
6) lubricating layer is CN-TiN nanometer crystal layer.
2. nitrogenize carbon back nano-composite coating diesel engine fuel-firing pump plunger as claimed in claim 1, it is characterized in that: the thickness of described composite coating is the 2.5-15 micron, wherein
1) joint thickness is the 10-30 nanometer;
2) supporting layer thickness is the 1-10 micron;
3) binder course II thickness is the 20-80 nanometer;
4) graded bedding thickness is the 100-500 nanometer;
5) transition region thickness is for being the 0.4-3 micron;
6) lubricating layer thickness is for being the 1-5 micron.
3. nitrogenize carbon back nano-composite coating diesel engine fuel-firing pump plunger as claimed in claim 1 or 2 is characterized in that: described supporting layer is the Cr/CrN laminated coating that Cr layer and CrN layer alternately consist of.
4. nitrogenize carbon back nano-composite coating diesel engine fuel-firing pump plunger as claimed in claim 1 or 2, it is characterized in that: described lubricating layer is the CN-TiN nanocrystalline composite coating that the TiN Nanocrystals Embedded consists of in amorphous CN: the nanocrystalline diameter of its TiN is 3-50nm.
5. the preparation method of a nitrogenize carbon back nano-composite coating diesel engine fuel-firing pump plunger as claimed in claim 1 is characterized in that: formed successively by following step:
1) to carrying out through the diesel engine fuel-firing pump plunger of chemical cleaning after aura cleans, at its surface deposition binder course I, this binder course I is the Cr layer;
2) the binder course I that obtained in the upper step deposits supporting layer, and this supporting layer is the Cr/CrN layer;
3) the supporting layer deposition binder course II that obtained in the upper step, this binder course II is the Ti layer;
4) the binder course II that obtained in the upper step deposits graded bedding, and this graded bedding is TiNx, and wherein the scope of X is 0＜X≤1;
5) graded bedding that obtained in the upper step deposits transition layer, and this transition layer is the TiN-CN layer;
6) transition layer that obtained in the upper step deposits lubricating layer, and this lubricating layer is CN-TiN nanometer crystal layer, naturally cooling, and get final product.
6. the preparation method of nitrogenize carbon back nano-composite coating diesel engine fuel-firing pump plunger as claimed in claim 5 is characterized in that: described supporting layer is the Cr/CrN laminated coating that Cr layer and CrN layer alternately consist of.
7. the preparation method of nitrogenize carbon back nano-composite coating diesel engine fuel-firing pump plunger as claimed in claim 5, it is characterized in that: described lubricating layer is the CN-TiN nanocrystalline composite coating that the TiN Nanocrystals Embedded consists of in amorphous CN.
8. such as the preparation method of the arbitrary described nitrogenize carbon back nano-composite coating diesel engine fuel-firing pump plunger of claim 5-7, it is characterized in that:
1) condition of described aura cleaning is: temperature is 150-500 ℃, under the ar gas environment;
2) sedimentary condition of described binder course I is: air pressure 0.005-0.5Pa, and voltage-700V arrives-1200V;
3) sedimentary condition of described supporting layer is: air pressure 0.3-0.5Pa, and voltage-50V arrives-250V;
4) sedimentary condition of described binder course II is: air pressure 0.005-0.5Pa, and voltage-600V is to 1200V;
5) sedimentary condition of described graded bedding is: progressively pass into nitrogen, nitrogen flow progressively increases, and range of flow is at 50-300sccm, and air pressure 0.1-2Pa, bias voltage are 50-300V;
6) sedimentary condition of described transition layer is: progressively pass into acetylene, the acetylene flow progressively increases, at 50-300sccm; Nitrogen flow gradually reduces simultaneously, progressively is reduced to 100sccm from 300sccm; Bias voltage 50-200V;
7) sedimentary condition of described lubricating layer is: bias voltage-50V arrives-250V, air pressure 0.1-2Pa.
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| CN201210366567.1A CN102865220B (en) | 2012-09-28 | 2012-09-28 | Engine fuel pump plunger with carbon nitride-based nano composite coating and manufacturing method thereof |
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| CN201210366567.1A CN102865220B (en) | 2012-09-28 | 2012-09-28 | Engine fuel pump plunger with carbon nitride-based nano composite coating and manufacturing method thereof |
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| GB2565320A (en) * | 2017-08-10 | 2019-02-13 | Yang Shicai | Gradient method to deposit hard and lubricant coatings |
| CN109898056A (en) * | 2019-03-13 | 2019-06-18 | 广东工业大学 | A kind of bulk metal based on PVD technique/metal-ceramic nano functionally gradient material (FGM) and its preparation method and application |
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| CN102865220B (en) | 2014-12-03 |
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