CN1207428C - Ti-Ni-Si ternary metal silicide alloy coating material - Google Patents

Ti-Ni-Si ternary metal silicide alloy coating material Download PDF

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CN1207428C
CN1207428C CNB031478875A CN03147887A CN1207428C CN 1207428 C CN1207428 C CN 1207428C CN B031478875 A CNB031478875 A CN B031478875A CN 03147887 A CN03147887 A CN 03147887A CN 1207428 C CN1207428 C CN 1207428C
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coating material
coating
metal silicide
coated material
wear
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CN1470670A (en
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王华明
张凌云
于荣莉
王影
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Beihang University
Beijing University of Aeronautics and Astronautics
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Beihang University
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Abstract

The present invention discloses an alloy coating material composed of Ti-Ni-Si three-element metal silicide, which comprises elements of Ti, Ni and Si. The coating material comprises the following chemical compositions: 28 to 58 wt% of Ti, 28 to 60 wt% of Ni and 4 to 16 wt% of Si. The constituent phase of the structure of the coating material comprises two-element metal silicide of Ti5Si3, three-element metal silicide of Ti2Ni3Si and a small quantity of intermetallic compounds of NiTi, TiNiSi and Ni3Ti. The coating material has hardness of HV500 to HV900, and dry sliding wear resistance at indoor temperature is 10 to 30 times of that of rolling bearing steel GCr15 treated by quenching and low temperature tempering and 80 to 180 times of that of titanium alloy Ti6Al4V; the coating material has wear resistant service temperature as high as 1000 DEG C. The coating material adopts a laser cladding method to form a coating on the surface of a mechanical kinematic pair component to realize component surface modification and restoration.

Description

Ti-Ni-Si ternary metal silicide alloy coated material
Technical field
The present invention relates to a kind of non-ferrous metal alloy material, more particularly be meant the corrosion resistant Ti-Ni-Si ternary metal of a kind of heat resistant and wear resistant silicide alloy coated material and on the metal component of machine, make the anti-corrosion coating of heat resistant and wear resistant.
Background of invention
In industry such as Aeronautics and Astronautics, machinery, iron and steel and Non-ferrous Metallurgy, oil, chemical industry, electric power, ocean, exist a large amount of frictional wear kinematic pair metal components of machine under conditions such as high temperature, burn into thermal etching, to bear the intensive frictional wear, use properties cooperations such as requiring the secondary components of machine of these movement of metallic to have excellent abrasive simultaneously can (room temperature and high temperature abrasive wear, adhesive wear, corrosive wear erosive wear, fretting wear etc.), good high-temperature antioxidant property, low frictional coefficient and excellent friction consistency.
Adopt means such as Surface Engineering, prepare one deck high temperature wearable anti-corrosion coated material at ferrous materials such as titanium alloy, superalloy, high temperature steel, austenitic stainless steel and other various metal mechanical motion pair component surfaces, being to solve and improve one of effective and the most most economical measure of performances such as high temperature kinematic pair component wear resistance at elevated temperature, corrosion resisting property, also is one of most effectual way of shortcoming such as solve the contour performance structured material of titanium alloy frictional coefficient height, wear resistance is low, high-temperature oxidation resistance is low, the high temperature and high speed friction is inflammable.
Aspect high temperature wearable anti-corrosion coated material system: thermospray low melting point self-fluxing alloy systems such as Ni-Cr-B-Si-C, Fe-Cr-Si-B, Fe-Cr-Si-B-C, because hot hardness is low, antioxidant property is poor, the tribology consistency is poor, fusing point is low, be difficult to use as the high temperature wearable anti-corrosion coating; Co-WC, NiCr-Cr 2C 3, CoCr-Cr 3C 2Deng hot spraying metal ceramic abrasion-resistant coating material systems such as carbide enhancings, have that the coating antioxidant property is poor, fragility is big, coating is not fine and close, coating and the part interface bond strength is low, coating is to shortcomings such as mating part serious wear, tribology consistency are low; Aluminum oxide, zirconia ceramics material high temperature wearable anti-corrosion coating, high temperature abrasion resistance and high-temperature oxidation resistance excellence, but its tribology consistency to metal is poor, and coating can only adopt heat spraying method preparations such as plasma spraying, coating structure is not fine and close, coating fragility is very big, and use can be very limited as the high-temperature wearable kinematic pair usually.
Aspect coat preparing technology: the coating of heat spraying method preparations such as flame plating, HVOF (High Velocity Oxygen Fuel), atmospheric plasma spraying spraying, low-voltage plasma spraying, electric arc spraying, detonation flame spraying, tissue exists loose and hole, particularly coating and metal parts interface junction are combined into mechanical bond, interface intensity is low, and coating is easily peeled off in high temperature friction and wear and thermal cycling process; Laser cladding method prepare coating exist organize tiny, composition is even, coating is fine and close, be characteristics such as complete metallurgical binding between coating and the metal parts base material, is one of Perfected process for preparing high-performance high-quality coating.
Summary of the invention
One of purpose of the present invention is to provide a kind of heat resistant and wear resistant anti-corrosion Ti-Ni-Si ternary metal silicide alloy coated material.
Another object of the present invention is to provide a kind of anti-corrosion coating of heat resistant and wear resistant that is used for making on the metal component of machine, the surface modification and the reparation of realization component.
A kind of Ti-Ni-Si ternary metal silicide alloy coated material of the present invention comprises Ti, Ni, Si element, and its chemical ingredients Ti is that 28～58wt%, Ni are that 28～60wt%, Si are 4～16wt%, and it mainly organizes composition to be ternary metal silicide Ti mutually 2Ni 3Si also contains compound N iTi and Ni between little metal 3It is ternary metal silicide Ti mutually that Ti or main tissue are formed 2Ni 3Si and Ti 5Si 3Or main tissue composition is ternary metal silicide Ti mutually 2Ni 3Si, and contain compound Ti between little metal 5Si 3, NiTi, TiNiSi and Ni 3Ti.
Described silicide alloy coated material, its chemical ingredients Ti are that 28～33wt%, Ni are that 55～59wt%, Si are 9.5～11wt%, and it mainly organizes composition to be Ti mutually 2Ni 3Si also contains small amount of N iTi and Ni 3Ti.
Described silicide alloy coated material, its chemical ingredients Ti are that 37～41wt%, Ni are that 48～52wt%, Si are 9.5～11wt%, and it mainly organizes composition to be Ti mutually 2Ni 3Si also contains Ti 5Si 3
Described silicide alloy coated material, its chemical ingredients Ti are that 42～46wt%, Ni are that 42～46wt%, Si are 10.5～12.5wt%, and it mainly organizes composition to be Ti mutually 2Ni 3Si also contains Ti 5Si 3
Described silicide alloy coated material, its chemical ingredients Ti are that 50～54wt%, Ni are that 30～34wt%, Si are 14～16wt%, and it mainly organizes composition to be Ti mutually 2Ni 3Si also contains Ti 5Si 3
Described silicide alloy coated material, its chemical ingredients Ti are that 33～37wt%, Ni are that 55～59wt%, Si are 5～8wt%, and it mainly organizes composition to be Ti mutually 2Ni 3Si also contains Ti 5Si 3
Described silicide alloy coated material, its chemical ingredients Ti are that 35～39wt%, Ni are that 55～59wt%, Si are 4～6wt%, and it mainly organizes composition to be Ti mutually 2Ni 3Si also contains small amount of N iTi and Ni 3Ti.
Described silicide alloy coated material, it also can add Cr or Mo or Al that total amount is no more than 12wt%.
The present invention is a preparation high-performance high temperature wearable anti-corrosion multi-functional coatings novel material on metallic substance mechanical motion pair component such as titanium alloy, superalloy, high temperature steel, stainless steel, aluminium alloy, low alloy steel, make component have the parts that performances such as excellent wear-resisting property (comprising excellent normal temperature and high temperature abrasive wear, adhesive wear, erosive wear, corrosion wear characteristic etc.), excellent high temperature oxidation resistance energy, low-friction coefficient, good metal friction consistency cooperate simultaneously, reach surface modification, effectively reduce cost.
Description of drawings
Fig. 1 is a room temperature dry sliding wear experimental principle synoptic diagram.
Fig. 2 is the organism optical metallograph of 4# alloy coating material, X500.
Fig. 3 is the organism optical metallograph of 6# alloy coating material, X500.
Fig. 4 is the Hardness Distribution curve of 3# alloy coating material.
Fig. 5 is the Hardness Distribution curve of 5# alloy coating material.
Embodiment
The present invention is a kind of Ti-Ni-Si ternary metal silicide alloy high temperature wearable anti-corrosion coated material, this coated material is mainly elementary composition by Ti, Ni, Si, its chemical ingredients is that the weight percent of Ti is 28～58, the weight percent of Ni is 28～60, the weight percent of Si is 4～16, for further improving the performances such as wear-resisting, anti-corrosion and obdurability of this alloy, also add total amount and be not more than 12% Cr or Mo or Al alloying element.It is ternary metal silicide Ti mutually that the main tissue of this coated material is formed 2Ni 3Si also contains compound N iTi and Ni between little metal 3It is ternary metal silicide Ti mutually that Ti or main tissue are formed 2Ni 3Si and Ti 5Si 3Or main tissue composition is ternary metal silicide Ti mutually 2Ni 3Si, and contain compound Ti between little metal 5Si 3, NiTi, TiNiSi and Ni 3Ti.This coated material has excellent normal temperature and high temperature abrasive wear and adhesive wear wear resistance, low frictional coefficient, excellent high-temperature oxidation resistance and hot corrosion resistance, excellent friction consistency and solidity to corrosion.
The hardness of this coated material is HV500～HV900, and room temperature dry sliding wear wear resistance is 10～30 times of quenching low-temperaturetempering rolling bearing steel GCr15, is 80～180 times of titanium alloy ti6al4v, and wear-resisting use temperature reaches as high as 1000 ℃.
This Ti-Ni-Si ternary metal silicide alloy high temperature wearable anti-corrosion coated material; can adopt methods such as argon gas atomizing, centrifugal atomizing, plasma rotating electrode atomizing to be prepared into powdered alloy; utilize methods such as plasma spraying, detonation flame spraying, built-up welding, flame plating, laser melting coating to prepare coating, also can adopt element powders compound laser cladding method under the argon shield condition, to prepare the high temperature wearable anti-corrosion coating at ferrous materials such as titanium alloy, superalloy, austenitic stainless steel and other metallic substance mechanical motion pair component surface.
This Ti-Ni-Si ternary metal silicide alloy high temperature wearable anti-corrosion coated material can be widely used in the ferrous materials such as titanium alloy, superalloy, stainless steel in the industrial equipments such as electric power, the energy, oil, chemical industry, Non-ferrous Metallurgy, ferrous metallurgy, aerospace and the surface modification and the reparation of other metallic substance high temperature friction and wear mechanical motion pair component.
Embodiment
Choose the typical Ti-Ni-Si ternary metal silicide alloy coated material of six optimization design in the table 1.
The preparation method:
(1) adopting precision is three kinds of element powders of electronic balance weighing Ti, Ni, Si of 0.1mg, and it is 60～320 orders that powder size requires;
(2) mix above-mentioned element powders;
(3) adopt laser cladding method and on the component of machine surface, making coated material under the argon shield condition.
(4) be chosen at BT20, BT9, Ti-6Al-4V titanium alloy, 1Cr18Ni9Ti stainless steel, GH4169 nickel base superalloy structured material is prepared the high temperature wearable anti-corrosion coating as carrier.
Table 1:Ti-Ni-Si ternary metal silicide alloy chemical composition content (wt%)
Element Weight percent (wt%)
1# 2# 3# 4# 5# 6#
Ti 32 39 44 52.5 35 37.3
Ni 58 50.5 44.2 32.2 57 57.2
Si 10 10.5 11.8 15.3 8 5.5
1, adopt laser cladding method to prepare coating
Selecting granularity for use is the above-mentioned powdered alloys of 60～320 purposes, at the TJ-5000 type 5kW continuous CO that flows over 2On Materialbearbeitung mit Laserlicht and the surface modification suite of equipment, adopt fore-put powder and synchronous powder feeding system method, utilize laser melting coating and under the argon shield condition on the carrier surface of the trade mark for the titanium alloy of BT20, BT9, Ti-6Al-4V, 1Cr18Ni9Ti stainless steel, GH4169 nickel base superalloy, 45 steel structure materials, preparation Ti-Ni-Si ternary metal silicide alloy coating.
The laser melting and coating process condition is: laser output power 2.5～3.5kW, the about 3～6mm of spot diameter size, beam flying speed are 200～350mm/min.Laser cladding coating dense structure evenly, flawless, pore-free, with between the part base material being complete metallurgical melting combination.
It is metal silicide Ti mutually that coating structure is mainly organized composition 2Ni 3Si, Ti 5Si 3And a small amount of TiNiSi or Ti 2Ni 3Si metal silicide and NiTi intermetallic compound and small amount of N i 3Ti and Ti 5Si 3Coating hardness is evenly distributed, average coating hardness HV500～HV900.
2, microstructure analysis
Adopt Dmax-2200pc rotating anode X-ray diffractometer that wear-resisting composite coating is carried out the thing phase composite and analyze, observe with carrying out coating structure analysis and worn surface on Neophot optical metallographic microscope and the S-530 scanning electronic microscope respectively.Measure coating average hardness and Hardness Distribution at the semi-automatic microhardness tester of MH-6.
X-ray diffraction analysis is the result show, it is metal silicide Ti mutually that the main tissue of 1# coated material is formed 2Ni 3Si and a small amount of Ti 5Si 3, NiTi, Ni 3Ti and TiNiSi; It is binary metal silicide Ti mutually that the main tissue of 2#～4# coated material is formed 5Si 3And ternary belongs to silicide Ti 2Ni 3Si, as shown in Figure 2, Ti wherein 5Si 3Percent by volume and coating hardness all improve with the raising of Ti content and Si content; The main tissue composition of 5#～6# coated material belongs to silicide Ti for ternary 2Ni 3Si and intermetallic compound NiTi also can contain small amount of N i 3Ti, as shown in Figure 3, Ti wherein 2Ni 3Mutually shared percent by volume of Si and coating hardness all improve with the raising of Si content.
3, room temperature dry sliding wear experiment
On MM-200 type wear test machine, carry out the dry sliding wear experiment, as shown in Figure 1.(be of a size of 10mm * 10mm * 10mm) and with quenching low-temperaturetempering rolling bearing steel GCr15# steel the mill test ring rubbed, cause specimen surface to wear and tear, the wear test parameter sees Table 2 to coated material.Respectively with quenching low-temperaturetempering rolling bearing steel GCr15 and titanium alloy ti6al4v as standard test specimen, adopt the wear weight loss of weighting method measurement standard sample and wearing and tearing sample, all clean sample before and after the wearing and tearing with alcohol, be 10 with sensibility reciprocal -4The electronic analytical balance of gram takes by weighing sample wear weight loss (all results are the mean value of three same sample), uses relative wear resistance ε wBeing that standard specimen is weightless is measurement sample wear resistance standard just, ε with likening to of sample weightlessness wBig more, the expression material wear ability is good more.
Table 2 skimming wear experiment parameter
Load (kg) is to bull ring speed of rotation (rpm) wearing-in period (min)
15.0 400 60
4, the microhardness of Ti-Ni-Si alloy coating material and wear resistance
Laser melting coating Ti-Ni-Si ternary metal silicide alloy coating hardness is evenly distributed, and coating hardness is very high, and average hardness reaches more than HV500～HV900, and the Hardness Distribution curve of several typical coating is seen Fig. 4 and Fig. 5.Wearing test result shows that this coated material has good wear resistance, and its wear resistance is 10～30 times of quenching rolling bearing steel GCr15, be 80～180 times of titanium alloy ti6al4v, and frictional coefficient reduces more than 30% than titanium alloy.
Table 3 coated material is with the room temperature dry sliding wear test-results of quenching rolling bearing steel GCr15
Alloy 1# 2#～4# 5#～6# GCr15
Before the wearing and tearing, gram 8.8876 7.7529 9.6301 8.1057
After the wearing and tearing, gram 8.8757 7.7485 9.6259 7.9639
Wear weight loss 0.0119 0.0044 0.0042 0.1418
Relative wear resistance 11.9 32.2 33.7 1.0
Table 4 coated material is with the room temperature dry sliding wear test-results of titanium alloy ti6al4v
Alloy 1# 2#～4# 5#～6# Ti6Al4V
Before the wearing and tearing, gram 8.8876 7.7529 9.6301 9.8009
After the wearing and tearing, gram 8.8757 7.7485 9.6259 8.8358
Wear weight loss 0.0119 0.0044 0.0042 0.9651
Relative wear resistance 81.1 219.3 229.7 1.0
In the described alloy coating material of table 1, add gross weight and be no more than 12% Cr or Mo or Al element powders, can effectively improve high temperature abrasion resistance, high-temperature oxidation resistance, solidity to corrosion and the hot strength of 1%～5% coated material.
Coated material of the present invention can be widely used in improving on the carrier of ferrous materials such as various titanium alloys, superalloy, high temperature steel, austenitic stainless steel in the industrial machineries equipments such as Aeronautics and Astronautics, weapons, boats and ships, electric power, the energy, oil, chemical industry, Non-ferrous Metallurgy, ferrous metallurgy and use propertieies such as other metallic substance frictional wear mechanical motion pair component are wear-resisting, anti-corrosion, heat-resisting, erosion resistance, reaches carrier surface modification and reparation.

Claims (9)

1, a kind of Ti-Ni-Si ternary metal silicide alloy coated material, it is characterized in that: comprise Ti, Ni, Si element, its chemical ingredients Ti is that 28～58wt%, Ni are that 28～60wt%, Si are 4～16wt%, and it mainly organizes composition to be ternary metal silicide Ti mutually 2Ni 3Si also contains compound N iTi and Ni between little metal 3It is ternary metal silicide Ti mutually that Ti or main tissue are formed 2Ni 3Si and Ti 5Si 3
2, silicide alloy coated material according to claim 1 is characterized in that: it is ternary metal silicide Ti mutually that main tissue is formed 2Ni 3Si, and contain compound Ti between little metal 5Si 3, NiTi, TiNiSi and Ni 3Ti.
3, silicide alloy coated material according to claim 1 is characterized in that: its chemical ingredients Ti is that 28～33wt%, Ni are that 55～59wt%, Si are 9.5～11wt%, and it mainly organizes composition to be Ti mutually 2Ni 3Si also contains small amount of N iTi and Ni 3Ti.
4, silicide alloy coated material according to claim 1 is characterized in that: its chemical ingredients Ti is that 37～41wt%, Ni are that 48～52wt%, Si are 9.5～11wt%, and it mainly organizes composition to be Ti mutually 2Ni 3Si also contains Ti 5Si 3
5, silicide alloy coated material according to claim 1 is characterized in that: its chemical ingredients Ti is that 42～46wt%, Ni are that 42～46wt%, Si are 10.5～12.5wt%, and it mainly organizes composition to be Ti mutually 2Ni 3Si also contains Ti 5Si 3
6, silicide alloy coated material according to claim 1 is characterized in that: its chemical ingredients Ti is that 50～54wt%, Ni are that 30～34wt%, Si are 14～16wt%, and it mainly organizes composition to be Ti mutually 2Ni 3Si also contains Ti 5Si 3
7, silicide alloy coated material according to claim 1 is characterized in that: its chemical ingredients Ti is that 33～37wt%, Ni are that 55～59wt%, Si are 5～8wt%, and it mainly organizes composition to be Ti mutually 2Ni 3Si also contains Ti 5Si 3
8, silicide alloy coated material according to claim 1 is on its feature: its chemical ingredients Ti is that 35～39wt%, Ni are that 55～59wt%, Si are 4～6wt%, and it mainly organizes composition to be Ti mutually 2Ni 3Si also contains small amount of N iTi and Ni 3Ti.
9, according to the described silicide alloy coated material of one of claim 1～7, it is characterized in that: also add Cr or Mo or Al that total amount is no more than 12wt%.
CNB031478875A 2003-06-30 2003-06-30 Ti-Ni-Si ternary metal silicide alloy coating material Expired - Fee Related CN1207428C (en)

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Publication number Priority date Publication date Assignee Title
CN100385028C (en) * 2006-05-09 2008-04-30 北京航空航天大学 High temperature wearable anti-corrosion Co-Ti-Si intermetallic compound alloy materials
CN100370051C (en) * 2006-05-09 2008-02-20 北京航空航天大学 High temperature wearable anti-corrosion Fe-Cr-Si iron base alloy materials
CN102030544B (en) * 2010-10-09 2012-09-05 北京航空航天大学 Preparation method of high temperature-resistant, radiation-insulated, heat-conducting and microwave-permeable inorganic coating
CN104152895B (en) * 2014-08-15 2016-04-13 山东大学 A kind of preparation technology of titanium alloy surface intermetallic compound base ceramic composite coating
CN105970021B (en) * 2016-07-05 2019-01-22 上海交通大学 A kind of anti-icing coatings and preparation method thereof
CN106747553B (en) * 2017-02-21 2019-12-27 西北工业大学 Method for realizing non-pressure connection between C/C composite materials
CN108517518B (en) * 2018-03-28 2020-05-22 中南林业科技大学 Preparation method of composite coating for improving high-temperature oxidation resistance of titanium alloy

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