CN100465347C - Drip-feed type gas boriding process - Google Patents
Drip-feed type gas boriding process Download PDFInfo
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- CN100465347C CN100465347C CNB2006100963866A CN200610096386A CN100465347C CN 100465347 C CN100465347 C CN 100465347C CN B2006100963866 A CNB2006100963866 A CN B2006100963866A CN 200610096386 A CN200610096386 A CN 200610096386A CN 100465347 C CN100465347 C CN 100465347C
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Abstract
This invention involves a drip gas boronizing approach. The method contains the steps of: adopting ordinary drip gas carburizing furnace, heating the furnace to the temperature for boronizing, and dropping boriding agent containing trimethyl borate, methanol and chloridated rare earth and methanol to the furnace, decomposing and to form boride on the steel surface through adsorption and diffusion of boron atom decomposed by trimethyl borate. The invention has the advantage of uniform and compact leaking layer, good surface quality, Layer depth and surface boron content can be controlled; no need of cleaning workpiece after infiltration, with directly quenching after infiltration and low labor intensity; penetration enhancers without rank poison, non-explosive, with relatively good and safe, reliable working environment, without specialized equipments, commonly used carburizing furnace can meet the requirements, can handle all sorts of shapes and sizes workpiece, can be easy to achieve automatic control, with high efficiency, easy operation and high applicability.
Description
Technical field
The present invention relates to the method for metal heat treatmet, more specifically to a kind of method of drip-feed type gas boriding.
Background technology
Boron is before the carbon that is positioned at second cycle in the periodic table of elements, atomic radius than carbon, nitrogen is big, with the ratio of magnesium-yttrium-transition metal atomic radius all greater than 0.59, so compound of forming of boron and magnesium-yttrium-transition metal has more than the mutually more complex crystalline structure in normal gap.This metallic compound such as FeB, Fe2B, TiB2, ZrB2, VB2, CrB2 hardness height, Heat stability is good, all higher than the hardness and the thermostability of corresponding carbide, nitride, but be difficult to cut, also be difficult to carry out other deformation processing.Common mechanical manufacturing steel can not add a large amount of boron in smelting process, the boron that can only add trace improves some performance of steel.The effect of boronising is that the boron content of steel surface is increased, so that can form the boride layer of high rigidity, this just makes the obdurability of matrix combine with the high hard wear-resisting erosion resistance on surface.After the steel part boronising, the boride that the top layer obtains is generally by the FeB+Fe2B two-phase, or the single-phase composition of Fe2B.This layer has high hardness, wear resistance, solidity to corrosion, red hardness and high temperature oxidation resistance.Hardness is the highest at 1500-2200HV after the iron and steel boronising, boride layer hardness height, thereby make the boronising part have high wear resistance, especially in abrasive wear, adhesive wear, and the tool and mould of working under the frictional wear condition, component of machine, the wear resistance after the boronising is far above the surface cementation or the nitrogenize of steel commonly used.
Since last century the '20s, boronizing technology (comprising boronizing agent and boriding process) has had than much progress, and boriding process existing and commonly used has: pack boriding, liquid boriding (electrolytic boriding and salt bath boronising), gas boriding (BCl
3Be enriched gas, H
2Be carrier gas), but they all have shortcoming.
Pack boriding is that powder (granular) boronizing agent is packed in the chest of heat-resisting steel, and steel part is imbedded wherein, then at air, vacuum or protective atmosphere (H
2Or Ar gas) heat the insulation boronising in the stove.Pack boriding is handled and do not needed Special Equipment, and is easy to operate, oozes back cleaning easily, and suitability is strong, is convenient to promote; But this method labour intensity is big, work under hard conditions, the penetration enhancer cost is also high, when workpiece is handled, penetration enhancer must fill up and ooze case, the penetration enhancer waste is serious, and the powder medium heat conductance is poor in addition, and heat-up time is long, power consumption is high, effect is low, difficulty is quite felt in the processing of large piece, and osmosis work-piece is difficult for taking out, and the direct quenching after being difficult to ooze is handled.The boronising of paste method is the development of solid powder boronisation, and powder boronizing agent is added that caking agent makes paste, is coated in the workpiece surface that needs boronising, adds thermodiffusion then.Although it has reduced the waste of penetration enhancer, other shortcomings still exist.
Gas boriding is with boronising gas BCl at present
3With hydrogen H
2Feed in the stove (BCI wherein
3Be boron supplying agent, H
2Be carrier gas), simultaneously stove is heated to the boronising temperature furnace gas is decomposed at workpiece surface, and then, spread and the formation boride by physicochemical absorption.The infiltration layer of gas boriding is even, fine and close, and surface quality is good, need not cleaning after workpiece oozes.Gaseous media is active in addition, can realize boronising at a lower temperature, and infiltration rate is also fast.But gases used preparation, preserve difficulty, cost an arm and a leg, severe toxicity is arranged and explosivity is arranged, still be difficult at present be used in industrial productio, under test basically.
Liquid boriding, at present commonly used have two kinds of electrolytic boriding and salt bath boronisings.
Electrolytic boriding is that workpiece is immersed in the borax bath of molten state, and is negative pole with the workpiece, and boronising is carried out in energising.The efficient height of electrolytic boriding, boronising at a lower temperature, boronizing agent is cheap, and depth of penetration is easy to control.But electrolytic boriding only is applicable to the part of simple shape, for complex-shaped part, because of each several part current density difference, can make boride layer in uneven thickness.Vitrified borax is serious to corrosion of crucible in addition, and the life-span is shorter.If the element in the crucible material is dissolved in the salt bath, then can influence the activity of salt bath boronizing agent, infiltration rate is descended.
The salt bath boronising is the more a kind of boronising of domestic application, and the main composition of boronizing agent is to be that matrix adds silicon carbide, silico-calcium, aluminium, ferrosilicon, reductive agents such as ferromanganese with borax or alkali-metal muriate.Also have in mentioned component and to add Sodium tetrafluoroborate.Add the salts of fluxing such as sodium-chlor, bariumchloride or carbonate in vitrified borax, it is simple, easy to operate to make the boronising temperature reduce to 700-800 ℃ of salt bath boronising equipment, and diffusion layer organization is controlled easily, and can handle shape than complicated parts.But the poor activity of salt bath, the workpiece cleaning difficulty, crucible life is short, and the homogeneity of salt temperature in mass production, the homogeneity of salt bath composition all be cannot say for sure to demonstrate,prove.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, design a kind of infiltration layer evenly, densification and labour intensity is low, good work environment and safety do not need Special Equipment a kind of drip-feed type gas boriding method, it is realized by following technical scheme:
Comprise the following steps:
A) boronising is prepared
Adopt common drop-feeding gas carburization stove, prepare boronizing agent earlier, the boronizing agent for preparing and methyl alcohol are injected respectively in the container that two of described cementing furnace holds drip liquid, to heating in the stove, when temperature in the stove rises to 740～760 ℃, beginning is instillation methyl alcohol and boronizing agent and exhaust in stove, and continues temperature in the process furnace;
B) workpiece shove charge
When temperature in the stove rises to 880～1000 ℃ of boronising temperature, will treat that workpiece that boronising is handled packs in the stove, shove charge finishes and continues temperature in the process furnace, and methyl alcohol and boronizing agent simultaneously instil;
C) surface boronizing
When temperature recovery in the stove during to described boronising temperature, workpiece surface begins boronising, according to the required alloying layer thickness difference of workpiece surface, keeps this boronising temperature 3～10 hours, at this process instillation boronizing agent, make described workpiece surface finally form boron sosoloid and boride;
D) quench treatment
After boronising finishes, stove is cooled to 860～880 ℃, and insulation, in this process, continue instillation methyl alcohol and boronizing agent, take out described workpiece then and place cooling fluid to quench at once, make workpiece surface form martensite and boride;
E) temper
Workpiece after boronising and the quenching is put into tempering stove immediately carry out tempering, 160～220 ℃ of tempering temperatures, tempering time 1.5～2.5 hours.
Described boronizing agent is prepared from by trimethyl borate, reductive agent and mixing diluents.
Described reductive agent is a rare earth chloride, and the weight ratio of rare earth chloride and boric acid three formicesters is 1:25～1:40 in described boronizing agent.
Described thinner is a methyl alcohol, the volumetric ratio 1:1～1:1.5 of methyl alcohol and boric acid three formicesters in described boronizing agent.
Described boric acid three formicesters can be obtained by the esterification reaction of boric acid and methyl alcohol.
The invention has the beneficial effects as follows: 1) infiltration layer is even, fine and close, and surface quality is good, depth of penetration and the equal may command of surperficial boron-containing quantity; 2) need not cleaning after workpiece oozes, and can ooze back direct quenching, labour intensity is low, the production efficiency height; 3) need not the preparation equipment of gas, cementing furnace commonly used can meet the demands, and can easily realize automatic control, and is easy to operate, can handle the workpiece of different shape and size, and it is low that suitability Johnson ﹠ Johnson produces cost; 4) penetration enhancer does not have severe toxicity, non-explosive, and Working environment is better relatively and safe and reliable.
Embodiment
Be the dropped amount that example provides boronizing agent, methyl alcohol all in following examples with the common drop-feeding gas carburization stove of 35kW.The drop-feeding gas carburization stove of other type can be adjusted according to the volume capacity difference.
Embodiment 1
Present embodiment pilot scale block of material is 45 steel; Test block size 30 * 20 * 10mm
3Boric acid three formicesters obtain by the esterification reaction of boric acid and methyl alcohol.
A) boronising is prepared
Volumetric ratio by 1:1 is measured trimethyl borate and methyl alcohol with measuring cup respectively, to weigh by the trimethyl borate that measuring cup is measured, press the weight ratio weighing rare earth chloride of rare earth chloride and trimethyl borate 1:25 again, above-mentioned trimethyl borate through weighing, methyl alcohol and rare earth chloride is mixed, make boronizing agent.
The above-mentioned boronizing agent that makes and methyl alcohol are poured into respectively in the container that two of cementing furnace holds drip liquid.Cementing furnace is heated, when temperature in the stove rises to 740 ℃, beginning instillation methyl alcohol and boronizing agent exhaust in stove, the methanol dropping amount is 70/min, is about the flow of 1.4ml/min, and the dropped amount of boronizing agent is 40/min, the flow that is about 0.8ml/min continues temperature in the process furnace simultaneously.
B) workpiece shove charge
When temperature in the stove rises to 880 ℃ of boronising temperature, pack in the stove treating workpiece that boronising is handled, shove charge finishes and continues temperature in the process furnace, methyl alcohol and boronizing agent simultaneously instil, the methanol dropping amount is 50/min, the flow that is about 1.0ml/min, the dropped amount of boronizing agent is 150/min, is about the flow of 3.0ml/min.
C) surface boronizing
When temperature recovery to 880 in the stove °, workpiece surface begins boronising, workpiece surface alloying layer thickness δ require be: 0.1≤δ≤0.2mm, kept this boronising temperature 3 hours, at this process instillation boronizing agent, the amount of dripping is 120/min, is about the flow of 2.0ml/min, methyl alcohol simultaneously instils, the amount of dripping is 30/min, is about the flow of 0.6ml/min, to keep furnace pressure in 10～12Pa scope, workpiece surface forms boron sosoloid and boride, its boronising thickness δ=0.14mm after the boronising;
D) quench treatment
After boronising finishes, stove is cooled to 860 ℃, and insulation 15min, continues instillation methyl alcohol and boronizing agent in this process, the amount of dripping is respectively 30,50/min, and flow is respectively 0.6,1.0ml/min.Take out described workpiece then and place oil cooling liquid to quench at once, make workpiece surface form martensite and boride, its hardness is 1640HV;
E) temper
Workpiece after boronising and the quenching is put into tempering stove immediately carry out tempering, tempering temperature is 160 ℃, and tempering time is 1.5 hours.
Embodiment 2
Present embodiment pilot scale block of material is 40Cr, test block size 30 * 20 * 10mm
3
A) boronising is prepared
At first prepare boronizing agent, volumetric ratio by 1:1.2 is measured methyl alcohol and trimethyl borate respectively, to weigh by the trimethyl borate that measuring cup is measured, press the weight ratio weighing rare earth chloride of rare earth chloride and trimethyl borate 1:32 again, above-mentioned trimethyl borate through weighing, methyl alcohol and rare earth chloride is mixed, make boronizing agent.
The above-mentioned boronizing agent that makes and methyl alcohol are poured into respectively in the container that two of cementing furnace holds drip liquid.Cementing furnace is heated, when temperature in the stove rises to 750 ℃, beginning instillation methyl alcohol and boronizing agent exhaust in stove, the methanol dropping amount is 75/min, is about the flow of 1.5ml/min, and the dropped amount of boronizing agent is 35/min, the flow that is about 0.7ml/min continues temperature in the process furnace simultaneously.
B) workpiece shove charge
When temperature in the stove rises to 940 ℃ of boronising temperature, pack in the stove treating workpiece that boronising is handled, shove charge finishes and continues temperature in the process furnace, methyl alcohol and boronizing agent simultaneously instil, the methanol dropping amount is 60/min, the flow that is about 1.2ml/min, the dropped amount of boronizing agent is 140/min, is about the flow of 2.8ml/min.
C) surface boronizing
When temperature recovery to 940 in the stove °, workpiece surface begins boronising, workpiece surface alloying layer thickness δ require be: 0.35≤δ≤0.5 μ m, kept this boronising temperature 6 hours, at this process instillation boronizing agent, the amount of dripping is 110/min, is about the flow of 2.2ml/min, methyl alcohol simultaneously instils, the amount of dripping is 45/min, is about the flow of 0.9ml/min, to keep furnace pressure in 14～16Pa scope, workpiece surface forms boron sosoloid and boride, its boronising thickness δ=0.43mm after the boronising;
D) quench treatment
After boronising finishes, stove is cooled to 870 ℃, and insulation 15min, in this process, continuing instillation methyl alcohol and boronizing agent, the amount of dripping is respectively 35,45/min, and flow is respectively 0.7ml/min, 0.9ml/min.Take out described workpiece then and place oil cooling liquid to quench at once, make workpiece surface form martensite and boride, its hardness is 1640HV;
E) temper
Workpiece after boronising and the quenching is put into tempering stove immediately carry out tempering, 190 ℃ of tempering temperatures, tempering time are 1.5 hours.
Embodiment 3
Present embodiment pilot scale block of material is 20 steel, test block size 30 * 20 * 10mm
3
A) boronising is prepared
At first prepare boronizing agent, volumetric ratio by 1:1.5 is measured methyl alcohol and trimethyl borate respectively, to weigh by the trimethyl borate that measuring cup is measured, press the weight ratio weighing rare earth chloride of rare earth chloride and trimethyl borate 1:40 again, above-mentioned trimethyl borate through weighing, methyl alcohol and rare earth chloride is mixed, make boronizing agent.
The above-mentioned boronizing agent that makes and methyl alcohol are poured into respectively in the container that two of cementing furnace holds drip liquid.Cementing furnace is heated, when temperature in the stove rises to 760 ℃, beginning instillation methyl alcohol and boronizing agent exhaust in stove, the methanol dropping amount is 80/min, is about the flow of 1.6ml/min, and the dropped amount of boronizing agent is 30/min, the flow that is about 0.6ml/min continues temperature in the process furnace simultaneously.
B) workpiece shove charge
When temperature in the stove rises to 1000 ℃ of boronising temperature, pack in the stove treating workpiece that boronising is handled, shove charge finishes and continues temperature in the process furnace, methyl alcohol and boronizing agent simultaneously instil, the methanol dropping amount is 70/min, the flow that is about 1.4ml/min, the dropped amount of boronizing agent is 130/min, is about the flow of 2.6ml/min.
C) surface boronizing
When temperature recovery to 1000 in the stove °, workpiece surface begins boronising, and it is 0.7≤δ≤0.85mm that workpiece surface alloying layer thickness δ requires, kept this boronising temperature 10 hours, at this process instillation boronizing agent, the amount of dripping is 100/min, is about the flow of 2.0ml/min, methyl alcohol simultaneously instils, the amount of dripping is 65/min, is about the flow of 1.3ml/min, to keep furnace pressure in 18～20Pa scope, workpiece surface forms boron sosoloid and boride, its boronising thickness=0.82mm after the boronising;
D) quench treatment
After boronising finishes, stove is cooled to 880 ℃, and insulation 15min, continues instillation methyl alcohol and boronizing agent in this process, the amount of dripping is respectively 40,40/min, and flow is respectively 0.8,0.8ml/min.Take out described workpiece then and place oil cooling liquid to quench at once, make workpiece surface form martensite and boride, its hardness is 2110HV;
E) temper
Workpiece after boronising and the quenching is put into tempering stove immediately carry out tempering, tempering temperature is 220) ° C, tempering time is 2 hours.
In the inventive method, methanol usage is more flexible, and when preparation increased as the ratio of the methyl alcohol of thinner during boronizing agent, the amount of dripping as the methyl alcohol of carrier gas in the boronizing process can correspondingly reduce, to guarantee having the active boron atom of capacity to be as the criterion in the stove.
The inventive method is to produce the gas boriding effect by the instillation mode, thus the boron atomic adsorption that trimethyl borate is decomposited, be diffused in workpiece surface form boride obtain even, fine and close, the boride layer that surface quality is good.The boron-containing quantity of infiltration layer can be controlled by the dropped amount of boronizing agent, the degree of depth of infiltration layer can be controlled by temperature in the stove and soaking time, whole gas boriding process is to carry out in existing common drop-feeding gas carburization stove, need not special gas and prepares equipment, can be easy to realize automatic control.Simultaneously, the workpiece after the boronising need not cleaning, oozes back direct quenching, reduces labour intensity greatly, has improved working conditions, the production efficiency height.In addition, penetration enhancer does not have severe toxicity, does not more have the sorrow of the explosivity in the existing gas boriding technology, and safety and production cost are low.
Claims (5)
1, the method for drip-feed type gas boriding is characterized in that comprising the following steps:
A) boronising is prepared
Adopt common drop-feeding gas carburization stove, prepare boronizing agent earlier, the boronizing agent for preparing and methyl alcohol are injected respectively in the container that two of described cementing furnace holds drip liquid, to heating in the stove, when temperature in the stove rises to 740～760 ° of C, beginning is instillation methyl alcohol and boronizing agent and exhaust in stove, continues temperature in the process furnace;
B) workpiece shove charge
When temperature in the stove rises to 880～1000 ° of C of boronising temperature, will treat that workpiece that boronising is handled packs in the stove, shove charge finishes and continues temperature in the process furnace, and methyl alcohol and boronizing agent simultaneously instil;
C) surface boronizing
When temperature recovery in the stove during to described boronising temperature, workpiece surface begins boronising, according to the required alloying layer thickness difference of workpiece surface, keeps this boronising temperature 3～10 hours, at this process instillation boronizing agent, make described workpiece surface finally form boron sosoloid and boride;
D) quench treatment
After boronising finishes, stove is cooled to 860～880 ° of C, and insulation, in this process, continue instillation methyl alcohol and boronizing agent, take out described workpiece then and place cooling fluid to quench at once, make workpiece surface form martensite and boride;
E) temper
Workpiece after boronising and the quenching is put into tempering stove immediately carry out tempering, 160～220 ℃ of tempering temperatures, tempering time 1.5～2.5 hours.
2, the method for drip-feed type gas boriding according to claim 1 is characterized in that described boronizing agent is prepared from by trimethyl borate, reductive agent and mixing diluents.
3, the method for drip-feed type gas boriding according to claim 2 is characterized in that described reductive agent is a rare earth chloride, and the weight ratio of rare earth chloride and boric acid three formicesters is 1:25～1:40 in described boronizing agent.
4, the method for drip-feed type gas boriding according to claim 2 is characterized in that described thinner is a methyl alcohol, the volumetric ratio 1:1～1:1.5 of methyl alcohol and boric acid three formicesters in described boronizing agent.
5, the method for drip-feed type gas boriding according to claim 2 is characterized in that described boric acid three formicesters can be obtained by the esterification reaction of boric acid and methyl alcohol.
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| CN102277553A (en) * | 2011-08-31 | 2011-12-14 | 镇江汇通金属成型有限公司 | Aluminum bronze drop soakage boriding process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1699617A (en) * | 2005-06-29 | 2005-11-23 | 上海大学 | Technological process for surface low temperature boriding of low carbon steel |
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| CN1699617A (en) * | 2005-06-29 | 2005-11-23 | 上海大学 | Technological process for surface low temperature boriding of low carbon steel |
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Assignee: Zhenjiang Huitong Metal Forming Co., Ltd. Assignor: Jiangsu University Contract record no.: 2010320000599 Denomination of invention: Drip-feed type gas boriding process Granted publication date: 20090304 License type: Exclusive License Open date: 20070425 Record date: 20100514 |
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