EP3751012A1 - Liquide de refroidissement - Google Patents

Liquide de refroidissement Download PDF

Info

Publication number
EP3751012A1
EP3751012A1 EP19460032.6A EP19460032A EP3751012A1 EP 3751012 A1 EP3751012 A1 EP 3751012A1 EP 19460032 A EP19460032 A EP 19460032A EP 3751012 A1 EP3751012 A1 EP 3751012A1
Authority
EP
European Patent Office
Prior art keywords
quenching
weight
solution
coolant
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP19460032.6A
Other languages
German (de)
English (en)
Inventor
Piotr GWIZD
Jerzy Stodolny
Marek Kedzierzynski
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Remix Spolka Akcyjna
Original Assignee
Remix Spolka Akcyjna
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Remix Spolka Akcyjna filed Critical Remix Spolka Akcyjna
Priority to EP19460032.6A priority Critical patent/EP3751012A1/fr
Publication of EP3751012A1 publication Critical patent/EP3751012A1/fr
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • 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

Definitions

  • the subject of the invention is a quenching coolant used in the processes of heat treatment of steel, in particular in the processes of quenching of steel with low hardening capacity, as well as for hyperquenching of other metals and their alloys.
  • State of the art consists of quenching coolants and quenching methods.
  • Quenching coolants are used in the processes of heat treatment of metals and metal alloys. These processes frequently require high-speed cooling, not always over the entire temperature range. This applies in particular to such treatments as e..g. quenching of steel.
  • the ranges of temperatures with required high cooling rate depend on the treated metal, its mass and shape.
  • quenching coolants including quenching oils, and water-based coolants containing various organic and inorganic compounds which change the cooling capacity of water during the quenching process.
  • Quenching coolant according to the invention forming a water solution of glycols and other organic and inorganic compounds, characterized in that it contains silicone oil, advantageously with cross-linked short-chains, in an amount of 5 to 25% by weight, dipropylene glycol in an amount of 20 to 50% by weight, sodium salt of polyacrylic acid with a molecular weight of 10000 - 100000 in an amount of 2 to 5% by weight, sodium salt of acrylic acid copolymer with a molecular weight 300000 - 1000000 in an amount of 0.1 to 2% by weight, polyoxyethylene stearate 1,4-sorbitol in an amount of 0.1 to 2% by weight, sodium salt of ortho-phenylphenol in an amount of 0.05 to 0.2% by weight, ⁇ -caprolactam poly(ethylene oxide) in an amount of 0.05 to 0.3% by weight and water in an amount making up to 100% by weight.
  • silicone oil advantageously with cross-linked short-chains
  • An agent for the preparation of water-based quenching baths is also known, shown in the patent description 117439.
  • This agent is characterized in that it contains from 30 to 80% by weight, advantageously from 45 to 55% by weight of cationic surfactant or a mixture of such surfactants, advantageously alcoxymethyl pyridinium halogens or quaternary ammonium or pyridinium compounds.
  • quenching bath concentrate containing 5-50% by weight of polyethylene glycols, 0.05%-0.2% of sodium triphosphate, 0.1-3.0% of sulfonates and water making up to 100%. Quenching bath based on this concentrate provides much better cooling in the upper range of temperatures than known non-oil-based quenching coolants and does not result in "soft stains" on the quenched surfaces.
  • the patent description 107518 presents an agent for quenching baths containing 40-80% of ethylene glycol or polyglycol ethers, 0.1-5% of sulfonates, 0.05%-4% of sodium triphosphate, 0.05-4% of colloidal silica as anti-foaming agent and 0.05-4% of poly(vinyl alcohol) in a water solution.
  • the agent's composition is specified by weight. This known agent enables volume quenching and surface induction quenching of low- and medium-alloy carbon steels and retains the ability to adjust cooling rate within a wide range.
  • This agent - intended mainly for high-alloy steels - is fundamentally a mixture of 20-70% by weight of polysaccharides, advantageously starch or its derivatives, and 80-30% by weight of water, and moreover may contain 0.05-5% of acridine compounds, 0.01-8% by weight of sodium hydroxide or tetraborate and 0.01-2% by weight of methyl phenyl silicone oil as anti-foaming agent.
  • Approximately 15% water solution of this known agent is characterized by a much more advantageous cooling curve for high-alloy steels than the cooling curve of OH-70 oil.
  • the patent description 151712 presents an agent for the preparation of quenching baths used in particular for high-grade tool steels.
  • the agent contains 10-80 parts by weight of polyacrylamide with high degree of polymerization, 0.05-10.5 parts by weight of triethanolamine, up to 5 parts by weight of formaldehyde and 20-90 parts by weight of water.
  • a quenching agent is also know, presented in the patent description 152073 - it forms a water solution from 2 to 10% of anionic polyacrylamide with high degree of polymerization, from 0.2 to 2.5% formaldehyde, from 0.5 to 5% of alcali metals polyphosphates or phosphates or phosphoric acid and from 0.5 to 7% of triethanolamine.
  • an agent for preparing of quenching baths for surface quenching of steel.
  • the agent is a water solution containing 20-40 parts by weight of triethanolamine, 10-45 parts by weight of ethylene glycol, 5-20 parts by weight of boric acid, 5-20 parts by weight of sodium tetraborate, 0.5-1 part by weight sodium tripolyphosphate and 0.05-1 part by weight of formaldehyde.
  • This invention is characterized by consisting of glycerine in an amount of 61-80% by weight, ethylene glycol in an amount of 1-20% by weight, polymerized sulphate free water solution of 6-8% polyacrylamide in an amount of 2-25% by weight and anhydrous sodium carbonate in an amount of 0-6% by weight in the solution of the agent.
  • the patent description 86772 presents a method for preparing a quenching bath concentrate, characterized in that 1 to 17% by weight of polyvinyl alcohol, 0.5 to 60% of glycerine and 30 to 95% by weight of water are stirred in a stirrer of any type or using ultrasound, until a uniform consistency of the concentrate is obtained over its entire volume, and then is heated to a temperature of 40 to 100 °C.
  • coolants which are polymer solutions, the attractiveness of which results from their intermediate cooling rate compared to oil and water, and an important advantage of water polymer solutions is their non-inflammability, which significantly improves operational safety in the quenching shop.
  • Cooling of steel in a liquid from austenitization temperature to the environment temperature is performed with a varying cooling rate.
  • the tested coolants water, oils, polymer solutions
  • three main ranges of cooling rate changes are observed for a probe heated to 850 °C:
  • the analogous cooling phases described above are supplemented with the deposition of polymer film near the surface of the cooled metal.
  • the deposition of the polymer film is related to the inversion of the polymer solution's concentration. This may be described in the most simple manner that with the increase of the solution temperature after passing through a specific maximum solubility temperature, the water solubility of polymer starts to decrease and it precipitates out of the solution. Many publications describe this phenomenon in polymer solutions [ L. Mandelkern - Crystallization od Polymers. Second Edition, Cambridge University press, 2002 ].
  • Inhibition of heat transfer through the polymer film in the initial cooling period (during the evaporation phase) has a negative impact and is usually undesirable, since it is advantageous to lower the temperature as fast as possible in the range of 850 to 450 °C, to bypass the "nose" of the initial change on the CTPc diagram.
  • One of the solutions used to eliminate this negative factor is intense stirring of the polymer bath. The flow of liquid rips away the polymer and steam layer, which increases the cooling speed.
  • coolants are matched to a specific heat treated material, therefore a wide range of coolants is used, such as: salt and alkaline water solutions, water, quenching oils (usually synthetic), polymer solutions, gasses, molten salts and molten metals.
  • coolants may be used with various cooling methods, e.g. by immersion in coolant baths, by liquid spraying, by gas blowing, in presses, in fluidised beds etc.
  • the fastest known immersion coolants are salt and alkaline water solutions.
  • the coolant characteristics of a 10% NaCl salt water solution are presented on Fig. 4 .
  • the maximum cooling speed of 260 °C/s was obtained at the temperature of 720 °C already.
  • the lack of evaporation period in the initial quenching period, right after the immersion of the probe in the quenching bath should also be noted.
  • the method of cooling and the coolant are selected not only for economic reasons, but also in order to minimise deformations after heat treatment. Therefore for non-alloy steels undergoing quenching, a rapid course of quenching from austenization point to the martensitic transformation point would be desirable, and further course of cooling should be performed at a lower rate, reducing the post-quenching stresses and deformations.
  • Cooling in a salt solution or in pure water is frequently not a good solution and leads to the occurrence of quenching cracks, whereas the use of one of the available quenching oils lead to an insufficient cooling rate.
  • the polymer solutions turned out to be an intermediate medium between water and oils, since they have varying cooling characteristics. They do not have the main disadvantage of oils, that is, the inclination to ignition and smoking. The polymer solutions are therefore safer to use and allow the adjustment of the heat collection ability by changing the solution's concentration.
  • the solution according to the invention eliminates the drawbacks and disadvantages known from the state of the art.
  • the essence of the invention which is a quenching coolant made as a water solution, consists of it containing from 0.001 to 2.0% by weight of carboxymethylcellulose NaCMC (sodium salt of cellulose glycolic acid), advantageously 0.5% by weight, and contains water in an amount making up to 100% by weight.
  • carboxymethylcellulose NaCMC sodium salt of cellulose glycolic acid
  • the solution contains distilled water
  • the quenching coolant contains germicidal and fungicidal agents, most advantageously in the form of oxazolidine - MBO, in an amount of 0.05 to 0.15% by weight, most advantageously 0.1% by weight.
  • the main ingredient for the biopolymer polyelectrolyte quenching coolant is the sodium salt of cellulose glycolic acid, that is, carboxymethylcellulose (NaCMC), which is an amorphous substance, easily dissolved in hot and cold water, forming stable solutions - in such an aquaeous solution NaCMC is a polyelectrolyte (a polyacid).
  • NaCMC carboxymethylcellulose
  • Carboxymethylcellulose is a semi-synthetic cellulose derivative widely used in the food industry (ingredient with the symbol of E466) as a thickener, emulsifier, dietary fibre, and in pharmaceutical processing used in an amount of 2-6% as a bonding agent for wet pelleting, and in tablets as a disintegrant.
  • Carboxymethylcellulose is environmentally friendly and biodegradable. The substance is not classified as hazardous. It is also used in the manufacturing of ointments and a hydrogel base.
  • carboxymethylcellulose has a wide variety of other uses, e.g. in the manufacture of paints (as a thickener) or in oil drilling.
  • Carboxymethylcellulose is relatively resistant to the action of microorganisms, however it may undergo depolimerisation. Carboxymethylcellulose solutions therefore may demonstrate a propensity for the growth of bacteria and fungi, therefore just as for quenching oils and other polymers being sold, it is recommended to use an additive or additives which inhibit the corrosion of quenching baths and microbial growth.
  • One of the solutions is the use of an additive containing oxazolidine - MBO, the addition of which to the solution in an amount of 0.05 to 0.15% by weight should sufficiently protect the bath against the adverse effect of microbial growth.
  • the quenching coolant in the example implementation prepared as a water solution, contains:
  • NaCMC sodium salt of cellulose glycolic acid
  • the tests intended to verify the industrial use of the invention were conducted during the performance of the quenching process for, among others, SB7 spring fasteners used to attach railway rails to sleepers.
  • the ivf SmartQuench instrument was used for the tests, equipped with an additional bath for the stirring of polymer liquids with adjustable speed - according to the ASTM D 6482 standard.
  • the tests were conducted using moving liquid, at a constant stirrer rotational speed of 1000 rpm.
  • the example quenching was performed under production conditions on SB7 spring fasteners. These fasteners were manufactured with 51Si7 grade medium-carbon steel, that is, with added silicon. The rods used for manufacturing were 16 mm in diameter.
  • the quenching was conducted using two versions of the solution, with a NaCMC concentration of respectively 0.3% and 0.5%, which form example implementations.
  • the second example implementation is quenching in a polymer solution with a NaCMC concentration of 0.5%. After quenching and tempering the following hardness measurement results were obtained: 46, 46 and 46 HRC. The examination of structure using a scanning microscope have demonstrated the presence of martensite tempered without any trace of proeutectoid ferrite, which also indicated that desired and correct results were obtained.
  • quenching coolant according to the invention in the form of a carboxymethylcellulose based polymer solution with a concentration of 0.3% (quenching performed under production conditions) allowed obtaining better results then the use of solutions known from the state of the art. After quenching and tempering the hardness in the following range was obtained: 44-45 HRC. The examination of structure using a scanning microscope have demonstrated the presence of martensite tempered without any trace of proeutectoid ferrite, which indicated that desired and correct results were obtained after the quenching using a new polymer solution with a concentration of 0.3%.
  • the conducted tests indicate that the use of quenching coolant acc. to the invention allows the effective conducting of heat treatment process for steels with low hardening capacity, since the main advantage of this coolant is the very high cooling speed in the upper quenching range, that is, between 850°C and 300°C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
EP19460032.6A 2019-06-11 2019-06-11 Liquide de refroidissement Withdrawn EP3751012A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP19460032.6A EP3751012A1 (fr) 2019-06-11 2019-06-11 Liquide de refroidissement

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP19460032.6A EP3751012A1 (fr) 2019-06-11 2019-06-11 Liquide de refroidissement

Publications (1)

Publication Number Publication Date
EP3751012A1 true EP3751012A1 (fr) 2020-12-16

Family

ID=67180729

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19460032.6A Withdrawn EP3751012A1 (fr) 2019-06-11 2019-06-11 Liquide de refroidissement

Country Status (1)

Country Link
EP (1) EP3751012A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL159862B1 (en) 1989-02-06 1993-01-29 Inst Mech Precyz Quenching fluid
CN104263886A (zh) * 2014-09-24 2015-01-07 中国石油化工股份有限公司 淬火液组合物及其用途
US20170247633A1 (en) * 2012-12-27 2017-08-31 Idemitsu Kosan Co., Ltd. Water-based coolant
CN108300924A (zh) * 2017-10-19 2018-07-20 靖江市新程汽车零部件有限公司 新型热成形加强件及其加工方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL159862B1 (en) 1989-02-06 1993-01-29 Inst Mech Precyz Quenching fluid
US20170247633A1 (en) * 2012-12-27 2017-08-31 Idemitsu Kosan Co., Ltd. Water-based coolant
CN104263886A (zh) * 2014-09-24 2015-01-07 中国石油化工股份有限公司 淬火液组合物及其用途
CN108300924A (zh) * 2017-10-19 2018-07-20 靖江市新程汽车零部件有限公司 新型热成形加强件及其加工方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
L. MANDELKERN: "Crystallization od Polymers", 2002, CAMBRIDGE UNIVERSITY PRESS
T. HOLMP. OLSSONE. TROELL: "A Handbook", 2012, SWEREA IVF, article "Steel and its Heat Treatment"
ZAKHAROV A V ET AL: "STUDY OF THE POSSIBILITIES OF USING POLYMER AGENT NA-CARBOXYMETHYL CELLULOSE FOR QUENCHING RAILS AND RAIL FASTENING COMPONENTS", METAL SCIENCE AND HEAT TREATMENT, SPRINGER, NEW YORK, NY, US, vol. 33, no. 3 / 04, 1 March 1991 (1991-03-01), pages 294 - 299, XP000272876, ISSN: 0026-0673, DOI: 10.1007/BF00776438 *

Similar Documents

Publication Publication Date Title
EP0149623B1 (fr) Polyoxazolines dans des milieux de trempe aqueux
CA1084822A (fr) Procede de refroidissement controle de metaux ferreux
CN102719629B (zh) 一种水溶性聚醚类淬火剂
CN104263886A (zh) 淬火液组合物及其用途
CN104630427A (zh) 一种淬火剂
CN102417955B (zh) 用于热模具钢的水溶性淬火介质
EP0179545B1 (fr) Liquide de trempe aqueux contenant des polyoxazolines et des polymères comprenant des groupes N-vinylhétérocycliques
US4404044A (en) Method of quenching
EP3751012A1 (fr) Liquide de refroidissement
US3475232A (en) Method of quenching
US4584033A (en) Method of quenching
CN1259435C (zh) 水溶性淬火介质
CN101134994A (zh) 弹簧钢淬火介质水基淬火液热处理工艺
JPH01259119A (ja) 金属合金の焼入れ用水溶液の冷却能の修正方法
CN114262773A (zh) 一种基于带咪唑环有机电解质的回火液
CN105803164A (zh) 一种钢丝的淬火方法
US3271207A (en) Heat treating process
EP2740807B1 (fr) Composition de fluide de trempe synthétique
EP0196836B1 (fr) Milieu de trempe pour métaux
EP1625240B1 (fr) Composition de fluide de trempe
CN106011403B (zh) 一种铸钢件正火液及铸钢件正火冷却工艺
CN108441607A (zh) 环保型轧制淬火液
CN108977633A (zh) 一种安全环保的钢铁铸造淬火剂
Totten et al. Quenching Fundamentals: Stability & Drag-Out of Polymers.
CN109477156B (zh) 水系淬火液组合物和使用其的金属材料的制造方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20210617