CN104388646A - Graphene type liquid quenching cooling medium as well as preparation method and application thereof - Google Patents
Graphene type liquid quenching cooling medium as well as preparation method and application thereof Download PDFInfo
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- CN104388646A CN104388646A CN201410768107.0A CN201410768107A CN104388646A CN 104388646 A CN104388646 A CN 104388646A CN 201410768107 A CN201410768107 A CN 201410768107A CN 104388646 A CN104388646 A CN 104388646A
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/56—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering characterised by the quenching agents
- C21D1/60—Aqueous agents
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Abstract
The invention discloses a graphene type liquid quenching cooling medium which is a mixed solution formed by uniformly dispersing 1-10 parts of graphene solid particles with the particle size being 0.01-100 microns into 100-10,000 parts of water or water-based quenching liquid or mineral oil type quenching liquid. A preparation method comprises the steps of processing graphene into micro-powder particles with the required particle size, and then uniformly dispersing the graphene solid particles into the water or water-based quenching liquid or mineral oil type quenching liquid according to a proportioning requirement. The graphene type liquid quenching cooling medium is applied to quenching cooling of metal parts and can meet the requirements on the mechanical property and the deformation precision of the metal parts.
Description
Technical field
The present invention relates to a kind of graphite ene-type liquid hardening heat-eliminating medium and preparation method and application.
Background technology
The various component overwhelming majority of composition mechanized equipment needs just can possess physics, chemistry and mechanical property required by people through quenching and tempering process.
Quenching process steel-iron components is heated to high temperature (>850 DEG C) to carry out austenitizing, then heat-eliminating medium (water, oil) is placed in rapidly, wish, in very short time (0 ~ several seconds), high temperature (850 DEG C ~ 1050 DEG C) metal parts is cooled to about 300 DEG C, to avoid austenite to the transformation of non-martensite; Below 300 DEG C, it is desirable to be chilled to room temperature with cooling rate more slowly, the distortion caused to structural stress during martensitic transformation and thermal stresses to avoid austenite and cracking.Only has satisfied such condition, the mechanical property that just can be satisfied with most and the component of minimal deformation.
Traditional liquid hardening heat-eliminating medium generally has two classes: a class is simple tap water or the water-based hardening liquid containing various additive; Another kind of is simple mineral oil or the mineral oil containing various additive.
The cooling characteristic of water is: not enough in hot stage (steam film) cooling power, too high in cold stage cooling power, therefore, handled part both easily produced soft spots, had again very large distortion, even ftractureed.Add various additive in water after, this situation makes moderate progress, but effect is unsatisfactory.And in use, easily there is chemical reaction and change character thus change the characteristic of water-based hardening liquid in additive wherein, thus in use needs its aged deterioration situation of close tracking monitor, use and handling cost higher.
The cooling characteristic of oil is: although have cooling characteristic more slowly at cold stage, be also significantly less than the expected value of people in the cooling power of hot stage.Little at the parts quenching deformation ratio water of oil quenching, but there is lower hardness, the defect that quench-hardened case is more shallow.Add various additive in oil after, this situation makes moderate progress, but effect is unsatisfactory.And in use, easily there is chemical reaction and change character thus the characteristic changing oil base hardening liquid in additive wherein, thus in use needs its aged deterioration situation of close tracking monitor, use and handling cost higher.
In a word, there is following shortcoming in above-mentioned quenching medium:
The shortcoming of water:
High temperature section cooling rate is slow, and low-temperature zone cooling rate is fast, and cause part soft spots and strain cracking, scrap rate is very high.Various water-based hardening liquid easily produce rotten, aging, poisonous, irritant, have pollution etc.In addition, the cooling characteristic of water and water-based hardening liquid is too responsive to the change of water temperature, and this is the important factor causing the part with step, groove and hole class to produce distortion.
The shortcoming of oil:
High temperature section cooling is slow, quenches do not get angry to a lot of steel grade; Easy generation cracking and polymerization and deterioration by oxidation, easily aging, working parts strap output lossy serious, quenching time oil smoke seriously polluted greatly, production environment severe, costly.
Traditional liquid heat-eliminating medium also has a kind of fatal defect, is exactly that its cooling power varies with temperature and the high susceptibility that changes.The consequence that this characteristic causes is: when processing the part with step, groove and hole class, flowing due to these site fluid is hindered and makes its temperature raise (heat conduction herein is not gone out), causing liquid cooling characteristic herein to change makes cooling power significantly reduce, thus produces soft spots and distortion.This is the obstacle that traditional liquid quenchant cannot overcome.
Above-mentioned medium common defects also has: rotten and aging in order to tackle, and often need measure viscosity, acid number, ash content, composition, cooling towers group and often need whole updating hardening liquid etc., cause use and handling cost high.
The problem on deformation that traditional liquid heat-eliminating medium produces can also be tolerated for the part that some precision are lower, and for modern times a large amount of precision manufactureing, because the material property of traditional liquid heat-eliminating medium determined, which kind of no matter add additive to be also difficult to change the particular attribute of its liquid substance when cooling, thus its quench cooled characteristic and stress deformation effect are difficult to reach gratifying effect, although various additive makes moderate progress to its deficiency, simultaneously with side effect.
Chinese patent application CN 104059618 A discloses a kind of engine graphene oxide water-free cooling and preparation method thereof, engine graphene oxide water-free cooling, the graphene oxide that the propylene glycol that the ethylene glycol, the weight percent that are 30 ~ 65% by weight percent are 30 ~ 65%, weight percent are 0.2 ~ 3%, weight percent be 0.2 ~ 2% silicone antifoam agent and weight percent be 0.7 ~ 8% composite corrosion inhibitor mix and stir to dissolving and obtaining water-free cooling.Not moisture in this cooling fluid, and have multiple components mixed configuration to form, cost is high, and stability is poor, and only can be applicable to engine, the scope of application is narrow.
Summary of the invention
The object of the invention is for overcoming above-mentioned the deficiencies in the prior art, a kind of graphite ene-type liquid hardening heat-eliminating medium and preparation method and application are provided, Graphene solia particle is joined in traditional liquid quenchant as additive, graphene uniform distribution in media as well, because Graphene has the maximum capacity of heat transmission, therefore in process of cooling, whole medium is all in same temperature state (almost not having temperature head between each microcosmos area of media interior), metal parts is in this quenchant and can ensures do not have temperature head between its each volume element, thus can metal parts be met, especially the requirement of high degree of accuracy metallic element mechanical property and deformation accuracy.
For achieving the above object, the present invention adopts following technical proposals:
A kind of graphite ene-type liquid hardening heat-eliminating medium, 1 ~ 10 part of Graphene solid particulate being 0.01 micron ~ 100 microns according to weight part granularity is dispersed in the mixed solution formed in 100 ~ 10000 parts of water or water-based hardening liquid.
Preferably, granularity is that 1 part of Graphene solid particulate of 0.01 micron is dispersed in the mixed solution formed in 100 ~ 10000 parts of water or water-based hardening liquid by weight.
Preferably, granularity is that 1 part of Graphene solid particulate of 0.05 micron is dispersed in the mixed solution formed in 100 ~ 10000 parts of water or water-based hardening liquid by weight.
Preferably, granularity is that 1 part of Graphene solid particulate of 0.1 micron is dispersed in the mixed solution formed in 100 ~ 10000 parts of water or water-based hardening liquid by weight.
Preferably, granularity is that 1 part of Graphene solid particulate of 0.5 micron is dispersed in the mixed solution formed in 100 ~ 10000 parts of water or water-based hardening liquid by weight.
Preferably, granularity is that 1 part of Graphene solid particulate of 1 micron is dispersed in the mixed solution formed in 100 ~ 10000 parts of water or water-based hardening liquid by weight.
Preferably, granularity is that 1 part of Graphene solid particulate of 5 microns is dispersed in the mixed solution formed in 100 ~ 10000 parts of water or water-based hardening liquid by weight.
Preferably, granularity is that 1 part of Graphene solid particulate of 10 microns is dispersed in the mixed solution formed in 100 ~ 10000 parts of water or water-based hardening liquid by weight.
Preferably, granularity is that 1 part of Graphene solid particulate of 20 microns is dispersed in the mixed solution formed in 100 ~ 10000 parts of water or water-based hardening liquid by weight.
Preferably, granularity is that 1 part of Graphene solid particulate of 100 microns is dispersed in 100 ~ 10000 parts of water or water-based hardening liquid by weight; The mixed solution formed in mineral oil or mineral oil rapid quenching liquid.
Preferably, 1 part of Graphene solid particulate is dispersed in the mixed solution formed in 100 ~ 10000 parts of water or water-based hardening liquid by weight, wherein, Graphene is made up of the Graphene mixing of following Different Weight part and granularity: 0.01 micron 0.3 part, 0.05 micron 0.1 part, 0.1 micron 0.1 part, 0.5 micron 0.1 part, 1 micron 0.1 part, 5 microns 0.1 part, 10 microns 0.1 part, 100 microns 0.1 part.
Preferably, 9 parts of Graphene solid particulates are dispersed in the mixed solution formed in 10000 parts of water or water-based hardening liquid by weight, wherein, Graphene is made up of the Graphene mixing of following Different Weight part and granularity: 0.01 micron 2 parts, 0.05 micron 1 part, 0.1 micron 1 part, 0.5 micron 1 part, 1 micron 1 part, 5 microns 1 part, 10 microns 1 part, 100 microns 1 part.
Preferably, 10 parts of Graphene solid particulates are dispersed in the mixed solution formed in 10000 parts of water or water-based hardening liquid by weight, wherein, Graphene is made up of the Graphene mixing of following Different Weight part and granularity: 0.01 micron 3 parts, 0.05 micron 1 part, 0.1 micron 1 part, 0.5 micron 1 part, 1 micron 1 part, 5 microns 1 part, 10 microns 1 part, 100 microns 1 part.
A kind of graphite ene-type liquid hardening heat-eliminating medium, 1 ~ 10 part of Graphene solid particulate that to comprise according to weight part granularity be 0.01 micron ~ 100 microns is dispersed in the mixed solution formed in 100 ~ 10000 parts of mineral oils hardening liquids.
Preferably, granularity is that 1 part of Graphene solid particulate of 0.01 micron is dispersed in the mixed solution formed in 100 ~ 10000 parts of mineral oils hardening liquids by weight.
Preferably, granularity is that 1 part of Graphene solid particulate of 0.05 micron is dispersed in the mixed solution formed in 100 ~ 10000 parts of mineral oils hardening liquids by weight.
Preferably, granularity is that 1 part of Graphene solid particulate of 0.1 micron is dispersed in the mixed solution formed in 100 ~ 10000 parts of mineral oils hardening liquids by weight.
Preferably, granularity is that 1 part of Graphene solid particulate of 0.5 micron is dispersed in the mixed solution formed in 100 ~ 10000 parts of mineral oils hardening liquids by weight.
Preferably, granularity is that 1 part of Graphene solid particulate of 1 micron is dispersed in the mixed solution formed in 100 ~ 10000 parts of mineral oils hardening liquids by weight.
Preferably, granularity is that 1 part of Graphene solid particulate of 5 microns is dispersed in the mixed solution formed in 100 ~ 10000 parts of mineral oils hardening liquids by weight.
Preferably, granularity is that 1 part of Graphene solid particulate of 10 microns is dispersed in the mixed solution formed in 100 ~ 10000 parts of mineral oils hardening liquids by weight.
Preferably, granularity is that 1 part of Graphene solid particulate of 20 microns is dispersed in the mixed solution formed in 100 ~ 10000 parts of mineral oils hardening liquids by weight.
Preferably, granularity is that 1 part of Graphene solid particulate of 100 microns is dispersed in the mixed solution formed in 100 ~ 10000 parts of mineral oils hardening liquids by weight.
Preferably, 1 part of Graphene solid particulate is dispersed in the mixed solution formed in 100 ~ 10000 parts of mineral oils hardening liquids by weight, wherein, Graphene is made up of the Graphene mixing of following Different Weight part and granularity: 0.01 micron 0.3 part, 0.05 micron 0.1 part, 0.1 micron 0.1 part, 0.5 micron 0.1 part, 1 micron 0.1 part, 5 microns 0.1 part, 10 microns 0.1 part, 100 microns 0.1 part.
Preferably, 9 parts of Graphene solid particulates are dispersed in the mixed solution formed in 10000 parts of mineral oils hardening liquids by weight, wherein, Graphene is made up of the Graphene mixing of following Different Weight part and granularity: 0.01 micron 2 parts, 0.05 micron 1 part, 0.1 micron 1 part, 0.5 micron 1 part, 1 micron 1 part, 5 microns 1 part, 10 microns 1 part, 100 microns 1 part.
Preferably, 10 parts of Graphene solid particulates are dispersed in the mixed solution formed in 10000 parts of mineral oils hardening liquids by weight, wherein, Graphene is made up of the Graphene mixing of following Different Weight part and granularity: 0.01 micron 3 parts, 0.05 micron 1 part, 0.1 micron 1 part, 0.5 micron 1 part, 1 micron 1 part, 5 microns 1 part, 10 microns 1 part, 100 microns 1 part.
Further, the preparation method of above-mentioned arbitrary technical scheme,
First, Graphene is machined to the micro powder granule of required granularity;
Secondly, according to ratio requirement, by Graphene solid micro-powder even particulate dispersion in water or water-based hardening liquid or mineral oils hardening liquid.
Further, the graphite ene-type liquid hardening heat-eliminating medium above-mentioned arbitrary technical scheme prepared is applied in the quench cooled of metal parts.
Water-based hardening liquid in the present invention and mineral oils hardening liquid are currently available products, all can buy in the market, not repeat them here.
To it has been found that at present and in the material utilized, Graphene has the maximum capacity of heat transmission.
The thermal conductivity of various material
| Material | Thermal conductivity w/mk |
| Graphene | 4800--5300 |
| Silver | 429 |
| Copper | 401 |
| Aluminium | 237 |
| Gold | 317 |
| Water | 0.54 |
| Transformer oil | 0.128 |
| Diesel oil | 0.12 |
As can be seen from numerical value in showing above, the capacity of heat transmission of Graphene is 12 times of silver, 13 times of copper, 21 times of aluminium, 16 times of gold, more than 9300 times of water, 38460 times of oil.
As everyone knows, the process of cooling of cooled material is actually the heat exchanging process of heat-eliminating medium and cooled material, and namely the heat of cooled material gives heat-eliminating medium by heat exchange mechanism transmission.From physics, the thermal conductivity of heat-eliminating medium is larger, and namely thermal conductivity is better, then cold faster of cooled material, and namely the cooling power of heat-eliminating medium is better.In all substances that nature has been found at present, Graphene has the strongest capacity of heat transmission, and namely Graphene has maximum thermal conductivity.
The strong major cause of Graphene thermal conductivity of the present invention is: 1) graphene molecules is the macromole with typical two-dimensional sheet structure, its yardstick close to or be less than the mean free path of phonons of crystalline material, the thermal conduction of system is no longer retrained by Fourier's law, and adopts great-jump-forward and non-confinement heat trnasfer; 2) fluctuation between fluid and whirlpool are strengthened; 3) sheet macromole can relax Transverse Temperature Gradient between fluid.Therefore, Graphene is best suited for as heat-eliminating medium.
In water, group water solution or mineral oil, add Graphene micro powder granule, utilize the impayable thermal conductivity of Graphene, Fast Cooling effect can be produced.Because Graphene uniform particles is distributed in the solution of water or oil, its maximum conductive force can make whole solution obtain the temperature of high uniformity, thus make each microcosmos area of solution have identical cooling power, and then each position of complicated shape part can be made can to obtain Homogeneous cooling and homogeneous performance.
Graphite ene-type liquid quenching medium is except above-mentioned major advantage, compared with traditional liquid quenchant, due in quench cooled process, wherein the maximum conductive force of equally distributed Graphene particle can make the temperature altitude of whole liquid even, therefore can delays liquid aging, increase the service life, cost-saving.
Accompanying drawing explanation
Fig. 1 is Graphene cooling characteristic figure;
Fig. 2 is 500 times, heart portion metallographic structure photo after Ф 40mm45 steel cools in graphite ene-type liquid quenching medium;
Fig. 3 is 500 times, heart portion metallographic structure photo after Ф 30mm45 steel cools in water-based quenching medium.
Embodiment
Below in conjunction with embodiment, the present invention is further described.
Each Example formulations is as following table (be unit according to weight part)
The making method of above-described embodiment is:
First, Graphene is machined to the micro powder granule of required granularity;
Secondly, according to ratio requirement, by Graphene solid micro-powder even particulate dispersion in water or water-based hardening liquid or mineral oils hardening liquid.
The graphite ene-type liquid hardening heat-eliminating medium above-mentioned arbitrary technical scheme prepared is applied in the quench cooled of metal parts.
As shown in Figure 2,500 times, heart portion metallographic structure photo after Ф 40mm45 steel cools in graphite ene-type liquid quenching medium, visible Ф 40mm45 steel core portion is all martensitic stucture.
As shown in Figure 2,500 times, heart portion metallographic structure photo after Ф 40mm45 steel cools in graphite ene-type liquid quenching medium, visible Ф 40mm45 steel core portion is all martensitic stucture, illustrates, in process of cooling, the transformation of austenite to non-martensite does not occur.
Employing traditional liquid is water base, mineral oils quenchant:
In mineral oils (fast quenching oil, bright quenching wet goods), quenching, is 45 steel equally, and as Ф 15mm, heart portion just inevitably occurs non-martensite microstructure, and this is unallowed in actual production.
Quenching in water-based hardening liquid, is 45 steel equally, and as Ф 20mm, heart portion just inevitably occurs non-martensite microstructure, and this is unallowed in actual production.
Contrast visible, the quenching effect of graphite ene-type liquid hardening heat-eliminating medium is better than traditional liquid quenchant far away.
Fig. 3 is 500 times, heart portion metallographic structure photo after Ф 30mm45 steel cools in water-based quenching medium.The proeutectoid ferrite that core structure is obviously more as seen.Illustrate and there occurs the transformation of austenite to non-martensite in process of cooling.
Comparison diagram 2 and Fig. 3, the organization factors that two width pictures are shown, can illustrate that the cooling power of graphite ene-type liquid quenching medium is obviously greater than traditional liquid quenchant effectively.
Although above-mentioned, the specific embodiment of the present invention is described; but not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various amendment or distortion that creative work can make still within protection scope of the present invention.
Claims (10)
1. a graphite ene-type liquid hardening heat-eliminating medium, is characterized in that, 1 ~ 10 part of Graphene solid particulate being 0.01 micron ~ 100 microns according to weight part granularity is dispersed in the mixed solution formed in 100 ~ 10000 parts of water or water-based hardening liquid.
2. graphite ene-type liquid hardening heat-eliminating medium as claimed in claim 1, is characterized in that, granularity is that 1 part of Graphene solid particulate of 0.01 ~ 100 micron is dispersed in the mixed solution formed in 100 ~ 10000 parts of water or water-based hardening liquid by weight.
3. graphite ene-type liquid hardening heat-eliminating medium as claimed in claim 1, it is characterized in that, 9 parts of Graphene solid particulates are dispersed in the mixed solution formed in 10000 parts of water or water-based hardening liquid by weight, wherein, Graphene is made up of the Graphene mixing of following Different Weight part and granularity: 0.01 micron 2 parts, 0.05 micron 1 part, 0.1 micron 1 part, 0.5 micron 1 part, 1 micron 1 part, 5 microns 1 part, 10 microns 1 part, 100 microns 1 part.
4. graphite ene-type liquid hardening heat-eliminating medium as claimed in claim 1, it is characterized in that, 10 parts of Graphene solid particulates are dispersed in the mixed solution formed in 10000 parts of water or water-based hardening liquid by weight, wherein, Graphene is made up of the Graphene mixing of following Different Weight part and granularity: 0.01 micron 3 parts, 0.05 micron 1 part, 0.1 micron 1 part, 0.5 micron 1 part, 1 micron 1 part, 5 microns 1 part, 10 microns 1 part, 100 microns 1 part.
5. a graphite ene-type liquid hardening heat-eliminating medium, 1 ~ 10 part of Graphene solid particulate that to comprise according to weight part granularity be 0.01 micron ~ 100 microns is dispersed in the mixed solution formed in 100 ~ 10000 parts of mineral oils hardening liquids.
6. graphite ene-type liquid hardening heat-eliminating medium as claimed in claim 5, is characterized in that, granularity is that 1 part of Graphene solid particulate of 0.01 ~ 100 micron is dispersed in the mixed solution formed in 100 ~ 10000 parts of mineral oils hardening liquids by weight.
7. graphite ene-type liquid hardening heat-eliminating medium as claimed in claim 5, it is characterized in that, 9 parts of Graphene solid particulates are dispersed in the mixed solution formed in 10000 parts of mineral oils hardening liquids by weight, wherein, Graphene is made up of the Graphene mixing of following Different Weight part and granularity: 0.01 micron 2 parts, 0.05 micron 1 part, 0.1 micron 1 part, 0.5 micron 1 part, 1 micron 1 part, 5 microns 1 part, 10 microns 1 part, 100 microns 1 part.
8. graphite ene-type liquid hardening heat-eliminating medium as claimed in claim 5, it is characterized in that, 10 parts of Graphene solid particulates are dispersed in the mixed solution formed in 10000 parts of mineral oils hardening liquids by weight, wherein, Graphene is made up of the Graphene mixing of following Different Weight part and granularity: 0.01 micron 3 parts, 0.05 micron 1 part, 0.1 micron 1 part, 0.5 micron 1 part, 1 micron 1 part, 5 microns 1 part, 10 microns 1 part, 100 microns 1 part.
9., as the preparation method of any one of claim 1-8 graphite ene-type liquid hardening heat-eliminating medium, it is characterized in that,
First, Graphene is machined to the micro powder granule of required granularity;
Secondly, according to ratio requirement, by Graphene solid micro-powder even particulate dispersion in water or water-based hardening liquid or mineral oils hardening liquid.
10. as the application of any one of claim 1-8 graphite ene-type liquid hardening heat-eliminating medium, it is characterized in that, described graphite ene-type liquid hardening heat-eliminating medium is applied in the quench cooled of metal parts.
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| JP2018150621A (en) * | 2017-03-10 | 2018-09-27 | 国立大学法人電気通信大学 | Coolant |
| CN113817903A (en) * | 2020-06-18 | 2021-12-21 | 宝钢金属有限公司 | Novel quenching medium for heat treatment |
| CN115747627A (en) * | 2022-10-25 | 2023-03-07 | 安徽华聚新材料有限公司 | High-hardness high-toughness high-chromium cast iron grinding ball and preparation method thereof |
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| CN115747627A (en) * | 2022-10-25 | 2023-03-07 | 安徽华聚新材料有限公司 | High-hardness high-toughness high-chromium cast iron grinding ball and preparation method thereof |
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| CN104388646B (en) | 2017-01-11 |
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