CN102428056A - Gas generant composition - Google Patents
Gas generant composition Download PDFInfo
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- CN102428056A CN102428056A CN2010800215501A CN201080021550A CN102428056A CN 102428056 A CN102428056 A CN 102428056A CN 2010800215501 A CN2010800215501 A CN 2010800215501A CN 201080021550 A CN201080021550 A CN 201080021550A CN 102428056 A CN102428056 A CN 102428056A
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- Prior art keywords
- gas
- generant composition
- gas generant
- nitrate
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
- C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Organic Chemistry (AREA)
- Air Bags (AREA)
Abstract
Disclosed is a gas generant composition containing a fuel and an oxidant, which can be used for an inflator for a vehicle airbag system, or the like. The gas generant composition is characterized in that the oxidant contains a basic copper carbonate, the basic copper carbonate content in the gas generant composition is more than 40% by mass but 60% by mass or less, and the following conditions (a)-(c) are satisfied. (a) The burning rate is not less than 7.0 mm/sec. (b) The gas generation efficiency is not less than 2.30 mol/100 g. (c) The amount of heat generated per 1 mole of the generated gas is not more than 100 kJ/mol.
Description
Technical field
The present invention relates to can be used for the gas generant composition of airbag apparatus for vehicle with producer gas generator etc.
Background technology
In recent years, for miniaturized, the lightweight of the airbag apparatus for vehicle realizing requiring constantly uprising, be necessary to reduce the temperature of combustion of gas-evolution agent with producer gas generator.Yet, cause the slack-off or gas generating capacity decline of combustionvelocity sometimes thus.In order to improve the problems referred to above, having considered increases the method for the amount that is filled in the gas-evolution agent in the producer gas generator, but has produced the miniaturized that can not realize producer gas generator, the problem of this original purpose of lightweight.In order to address the above problem, be index preferably with " thermal discharge of every generation 1mol gas ".Usually, preferably at the thermal discharge of realizing every generation 1mol gas in below about 100kJ/mol, realize suitable combustionvelocity, gas luminous efficiency.
In JP-A 2004-155645, put down in writing: the basic metal nitrate that will be selected from basic copper nitrate, alkali formula Xiao Suangu, alkali formula zinc nitrate, alkali formula manganous nitrate, alkali formula iron nitrate, alkali formula nitric acid molybdenum, Vikaline and alkali formula cerous nitrate is as oxygen containing oxidant, and can reach the purpose that suppresses thermal discharge through adding white lake.
In JP-A 2001-220282, put down in writing: can use the basic metal nitrate that is selected from basic copper nitrate, alkali formula Xiao Suangu, alkali formula zinc nitrate, alkali formula manganous nitrate, alkali formula iron nitrate, alkali formula nitric acid molybdenum, Vikaline and alkali formula cerous nitrate as oxygenant.
In JP-B 3907548, put down in writing the oxygen containing oxidant that is selected from metal nitrate, an ammonium nitrate, metal perchlorate, ammoniumper chlorate, metal nitrite, metal chlorate, basic copper nitrate, alkali formula Xiao Suangu, alkali formula zinc nitrate, alkali formula manganous nitrate.
In JP-A 2006-76849; The content of having put down in writing ventilation breather surpasses 20 weight % and is the gas generant compositions below the 40 weight %; But because the content of ventilation breather among the embodiment is merely 22.0 weight %, the content that therefore can not confirm ventilation breather is the effects of 30 weight % when above.
Summary of the invention
Guarantor of the present invention topic is: provide a kind of in above-mentioned prior art, fully solve always can be used for the gas generant composition of airbag apparatus for vehicle with producer gas generator etc.; This gas generant composition does not damage combustionvelocity and gas luminous efficiency; Can reduce the thermal discharge of every generation 1mol gas, and also not have problems aspect the fume amount that when burning, produces, harmful gas concentration.
The present invention 1 provides a kind of gas generant composition; It contains fuel and oxygenant; Wherein, Oxygenant contains ventilation breather, and the content of the ventilation breather in the said gas generant composition surpasses 40 quality % and is below the 60 quality %, and this gas generant composition satisfies following condition (a)～(c):
(a) combustionvelocity is that 7.0mm/ is more than second;
(b) the gas luminous efficiency is more than the 2.30mol/100g;
(c) thermal discharge of every generation 1mol gas is below the 100kJ/mol.
Detailed Description Of The Invention
Gas generant composition of the present invention; Through utilizing the ventilation breather of specialized range amount; Do not damage combustionvelocity, gas luminous efficiency; Can reduce the thermal discharge of every generation 1mol gas, and also not have problems aspect the fume amount that when burning, produces, harmful gas concentration, therefore useful with producer gas generator etc. to airbag apparatus for vehicle.
The present invention includes following preferred implementation 2 to 6.
2. the described gas generant composition of the invention described above, wherein, the content of said ventilation breather is 42～60 quality %.
3. the described gas generant composition of the invention described above, wherein, said oxygenant is the combination of ventilation breather and basic metal nitrate and/or nitrate salt, and the total content of oxygenant is 50～80 quality %.
4. the described gas generant composition of the invention described above, wherein, said oxygenant is the combination of ventilation breather, basic copper nitrate and/or strontium nitrate, and the total content of oxygenant is 50～80 quality %.
5. the described gas generant composition of the invention described above, it further contains the carboxymethyl cellulose salt as sticker.
6. the described gas generant composition of the invention described above, it further contains white lake.
Gas generant composition of the present invention or for example gone for by the formed body of said composition gained: the driver air-bag of the various vehicles is used producer gas generator with producer gas generator, tubular system with producer gas generator, preloader with producer gas generator, inflatable seat belt with producer gas generator, kneepad with producer gas generator, curtain type gas bag with producer gas generator, copilot's gas generator for air bag, installing side airbag.
In addition; Use gas generant composition of the present invention or can be following any type by the producer gas generator of the formed body of said composition gained: only with the firework type of gas-evolution agent as the gas supply source, and with the pressurized gas of argon gas etc. and the gas-evolution agent mixed type as the gas supply source.
Further, gas generant composition of the present invention or can also expand the agent use of catching fire that combustion medicament (enhancer, booster) waits to being called as of gas-evolution agent the transmission ofenergy of lighter for ignition or ignitron as being used for by the formed body of said composition gained.
< fuel >
The fuel that uses among the present invention can use as the fuel of gas generant composition and known fuel for example can be enumerated: be selected from guanidine compound, tetrazole compound, compound in triazine class, purine compound or the amino acid derivative more than a kind.
Guanidine compound is preferably Guanidinium nitrate, nitroguanidine, N-guanylurea Zoamix salt etc.Tetrazole compound is preferably 5-amino tetrazole, two tetrazolium ammonia salt etc.Compound in triazine class is preferably the nitro-compound of trimeric cyanamide, melamine cyanurate, trimeric cyanamide nitrate salt, trimeric cyanamide perchlorate, three diazanyl s-triazine, trimeric cyanamide etc.Purine compound is preferably 8-azaguanine etc.Amino acid derivative is preferably glycocoll etc.
The fuel that uses among the present invention also can use the mixture more than 2 kinds or 2 kinds as required.Be preferably the mixture of the guanidine compound more than 2 kinds or 2 kinds or the mixture of guanidine compound and other species compound.For example, use separately under the situation of Guanidinium nitrate, though thermal discharge can be lower, existing problems aspect combustionvelocity, ignition quality.On the other hand, use separately under the situation of nitroguanidine,, have the lower problem of gas luminous efficiency though do not having problems aspect combustionvelocity, the ignition quality.To the problems referred to above,, can be brought into play both advantages effectively and overcome the fuel of both shortcomings through Guanidinium nitrate and nitroguanidine are mixed.
The content of the fuel that uses among the present invention is preferably 20～60 quality % in the gas generant composition, and more preferably 25～55 quality % further are preferably 30～50 quality %.
< oxygenant >
The oxygenant that uses among the present invention contains ventilation breather.The content of ventilation breather surpasses 40 quality % in the gas generant composition and is below the 60 quality %, is preferably 42～60 quality %.Under the situation below the 40 quality %, the effect that reduces thermal discharge is insufficient, surpasses under the situation of 60 quality %, and ignition quality suffers damage.
The median size of ventilation breather is preferably below the 5 μ m, more preferably below the 3 μ m, further is preferably below the 1 μ m.Under the big situation of median size, combustionvelocity is slack-off, and ignition quality worsens.Median size can be measured through the size-grade distribution method of utilizing laser light scattering light.Measure the MICROTRAC that uses Neede+Northrop Company to make; Model No.9320-X100 particle size measurement device; With sample dispersion in ion exchanged water; Ultrasonic irradiation with 50 watts of power is used for measuring for 60 seconds then, obtains 50% accumulated value of particle volume, with the MV of measuring gained for 2 times as median size.
Oxygenant further can contain as oxygenant and known material can contain the oxygenant more than a kind or a kind that is selected among nitrate salt, basic metal nitrate, an ammonium nitrate, metal perchlorate, ammoniumper chlorate, metal nitrite, the metal chlorate etc.
As basic metal nitrate; Can enumerate be selected from basic copper nitrate, alkali formula Xiao Suangu, alkali formula zinc nitrate, alkali formula manganous nitrate, alkali formula iron nitrate, alkali formula nitric acid molybdenum, Vikaline, the alkali formula cerous nitrate etc. more than a kind or a kind, be preferably basic copper nitrate.
As nitrate salt, can enumerate in alkine earth metal nitrates such as the base metal nitrate that is selected from saltpetre, SODIUMNITRATE etc., strontium nitrate etc. more than a kind or a kind, be preferably strontium nitrate.
The total content of the oxygenant that uses among the present invention is preferably 50～80 quality % in the gas generant composition, and more preferably 50～75 quality % further are preferably 50～70 quality %.
< sticker >
Gas generant composition of the present invention can contain as the sticker of gas generant composition and known material as required.For example can enumerate: be selected from CMC 99.5 (CMC), sodium carboxymethyl-cellulose (CMCNa), carboxymethyl-cellulose potassium salt (CMCK), carboxymethyl-cellulose ammonium salt (CMCNH
4); Rhodia; Cellulose acetate butyrate (CAB); Methylcellulose gum (MC); TKK 021 (EC); Natvosol (HEC); Type 3U (EHEC); Hydroxypropylcellulose (HPC); Carboxymethylethylcellulose (CMEC); Microcrystalline Cellulose; SEPIGEL 305; The amides of SEPIGEL 305; Polyacrylic hydrazide; Acrylamide-acrylic acid metallic salt copolymer; The multipolymer of SEPIGEL 305-ROHM ester cpds; Z 150PH (PVA); Acrylic rubber; Guar gum; Starch; In the ZGK 5 more than a kind or a kind.
As sticker, preferably as water-soluble cellulose derivative (CMC, CMCNa, CMCK, the CMCNH of water-soluble binder
4, MC, EC, HEC, EHEC, HPC, CMEC), Microcrystalline Cellulose, PVA, guar gum, starch.Wherein be preferably water-soluble cellulose derivative, more preferably CMC, CMCNa, CMCK, CMCNH
4, further be preferably CMCNa.
The content of the sticker that uses among the present invention adds up to 100 mass parts to be preferably 0.5～30 mass parts with respect to fuel and oxygenant, and more preferably 1～20 mass parts further is preferably 2～15 mass parts.
< additive >
Gas generant composition of the present invention can contain combustioncatalysts, heat absorbent, slag forming agent, lubricant etc. as required as the additive of gas generant composition and known material.As known additive, can enumerate: the MOX that comprises cupric oxide, red stone, zinc oxide, powder blue, manganese oxide, molybdenum oxide, nickel oxide, bismuth oxide, silicon-dioxide, aluminum oxide; The metal hydroxides that comprises white lake, cobaltous hydroxide, ironic hydroxide, Marinco H etc.; The metal carbonate or the basic metal carbonate that comprise cobaltous carbonate, lime carbonate, zinc subcarbonate; Comprise the MOX of acidic white earth, kaolin, talcum, wilkinite, zeyssatite, hydrotalcite or the complex chemical compound of oxyhydroxide; Metal acid-salt, ZGK 5, molybdenumdisulphide, calcium stearate, silicon nitride, silit, boric acid, metaboric acid, anhydrous boric acids etc. such as primary ammonium phosphate, ammonium polyphosphate, water glass, mica molybdate, cobalt molybdate, ammonium molybdate.
The content of additive of using among the present invention is not so long as make thermal discharge of the present invention, gas luminous efficiency, these effects of combustionvelocity receive big effect and get final product; Add up to 100 mass parts with respect to fuel and oxygenant; Be preferably 0.5～30 mass parts; More preferably 1～25 mass parts further is preferably 2～20 mass parts.
Gas generant composition of the present invention satisfies following condition (a)～(c) fully, and (d) preferably further satisfies condition.
(a) combustionvelocity is 7.0mm/ more than second, is preferably 7.4mm/ more than second;
(b) the gas luminous efficiency is more than the 2.30mol/100g, is preferably more than the 2.37mol/100g;
(c) thermal discharge of every generation 1mol gas is below the 100kJ/mol, is preferably below the 90kJ/mol;
(d) temperature of combustion is preferably below the 2000K, more preferably below the 1800K.
Compsn of the present invention can be shaped to desirable shape, can become cylindric, single hole is cylindric, porous circular cylinder shape or flaky formed body.
Said formed body can be through adding water or organic solvent and mix in compsn, the method for extrusion moulding (cylindric, single hole is cylindric, the formed body of porous circular cylinder shape) or make through the method (flaky formed body) of using tablet machine etc. to be compressed into type.
Embodiment
< mensuration of combustionvelocity >
[measuring making method] with powder column
With each composition of gas generant composition with the ratio thorough mixing shown in the table 1 after, weighing 30g.Add 6g water, in the anti-static polythene bag, mix more than 5 minutes, then the gained piece is processed thin small pieces, and 110 ℃ dry 2 hours down, pulverize with mortar then, obtain powder.This powder 1.7～2.2g is packed in the mould, apply about 220MPa (2250kgf/cm through oil pump
2) pressure, kept for 5 seconds after, obtain columned powder column (external diameter 9.55mm, length 12.70mm).
[measuring method]
Will be by the mensuration of above-mentioned gained with powder column 110 ℃ of held 16 hours, remove moisture, then in the side and the tackiness agent " Bond Quick 30 " of 2 epoxy resin systems of other end coating, make and only fire burns from end face.It is arranged on stainless steel (SUS) makes in the airtight pump (internal capacity 1L),, be forced into 7MPa on one side on one side to carrying out nitrogen replacement in the pump.After the pump internal pressure is stable, the nichrome wire that contacts with an end face of measuring with powder column is applied voltage 12V, utilize its energy that fuses that powder column is caught fire or burn.Rise to peak value institute elapsed time divided by beginning to pressure with the length of powder column with the mensuration before the burning from burning, with the value of calculating as combustionvelocity.
[thermal discharge of gas luminous efficiency, every generation 1mol gas, the calculating of temperature of combustion]
The thermal discharge of gas luminous efficiency, every generation 1mol gas and temperature of combustion are calculated through thermochemical equilibrium computation program " NEWPEP ".
[measuring method of the friction sensitivity and the impact sensitivity that drops hammer]
Weighing constitutes each powder stock of gas generant composition, and the quality that makes gas generant composition is 1g, with its thorough mixing.Measure the friction sensitivity of gained powdered sample and the impact sensitivity that drops hammer based on the gunpowder class PT method of the K4810-1979 of JIS (JIS).
[measuring method of decomposition temperature]
Use and the measuring method identical gas generant composition of friction sensitivity with the impact sensitivity that drops hammer; Carry out thermogravimetric analysis (Thermogravimetry) with thermobalance (Seiko Epson make TGDTA6300), the temperature that quality is begun to reduce is as decomposition temperature.
[measuring method of vent gas bulk concentration]
To use with the mensuration of above-mentioned same method gained with powder column (external diameter 9.55mm, quality 2.00g) 110 ℃ of held 16 hours; Remove moisture; Be arranged on stainless steel (SUS) then and make in the airtight pump (internal capacity 1L),, be forced into 7MPa on one side on one side to carrying out nitrogen replacement in the pump.After the pump internal pressure is stable, predetermined electric current is flow through and a nichrome wire that end face contacts of measuring with powder column, utilize its energy that fuses that it is caught fire or burn.After 60 seconds, gather the discharge gas that produces, utilize gas detector (GV-100S of GASTEC manufactured) and gastic reactotube (No.10:NO usefulness, No.3L and the 3M:NH of GASTEC manufactured
3Detection usefulness, No.1L:CO use) the mensuration gas concentration.
Embodiment and comparative example
Various mensuration shown in each compsn shown in the his-and-hers watches 1 carry out table 1.
GN: Guanidinium nitrate
NQ: nitroguanidine
GUDN:N-guanylurea Zoamix salt
Mel: trimeric cyanamide
MC: melamine cyanurate
BCC: ventilation breather (the about 1 μ m of median size)
BCN: basic copper nitrate
SrN: strontium nitrate
CMCNa: sodium carboxymethyl-cellulose
Al (OH)
3: white lake
The ventilation breather that endothermic effect is big although embodiment 1～23 has used a large amount of (surpassing below 40 quality % and the 60 quality %); But still the thermal discharge that can confirm every generation 1mol gas has obtained abundant inhibition (below the 100kJ/mo), and do not damage practical combustionvelocity (7.0mm/ is more than second) and gas luminous efficiency (more than the 2.30mol/100g).In contrast to this, a certain insufficient in the gas luminous efficiency of comparative example 1～8 or the combustionvelocity can think existing problems aspect practicality.
Various mensuration shown in each compsn shown in the his-and-hers watches 2 carry out table 2.
Can know that by table 2 friction sensitivity is in the JIS grade safest 7 grades or be 6 grades of can operate fully safely.In addition, the impact sensitivity that drops hammer is in the JIS grade safest 8 grades.Further, the temperature that begins to decompose is more than 150 ℃, is the TR that begins to decompose of in the time can tolerating the manufacturing producer gas generator, welding.Can find out by above, the dangerous reduction, and can make safely, and have practicality.
Various mensuration shown in each compsn shown in the his-and-hers watches 3 carry out table 3.
Can find out by table 3, at discharge gas NO, NH as obnoxious flavour
3Do not have problems with the concentration aspect of CO.
Claims (6)
1. gas generant composition; It contains fuel and oxygenant; Wherein, Said oxygenant contains ventilation breather, and the content of the ventilation breather in the said gas generant composition surpasses 40 quality % and is below the 60 quality %, and this gas generant composition satisfies following condition (a)～(c):
(a) combustionvelocity is that 7.0mm/ is more than second;
(b) the gas luminous efficiency is more than the 2.30mol/100g;
(c) thermal discharge of every generation 1mol gas is below the 100kJ/mol.
2. gas generant composition according to claim 1, wherein, the content of said ventilation breather is 42～60 quality %.
3. gas generant composition according to claim 1 and 2, wherein, said oxygenant is the combination of ventilation breather and basic metal nitrate and/or nitrate salt, and the total content of oxygenant is 50～80 quality %.
4. gas generant composition according to claim 1 and 2, wherein, said oxygenant is the combination of ventilation breather, basic copper nitrate and/or strontium nitrate, and the total content of oxygenant is 50～80 quality %.
5. according to each described gas generant composition in the claim 1～4, it further contains the carboxymethyl cellulose salt as sticker.
6. according to each described gas generant composition in the claim 1～5, it further contains white lake.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009122918A JP5441497B2 (en) | 2009-05-21 | 2009-05-21 | Gas generant composition |
| JP2009-122918 | 2009-05-21 | ||
| PCT/JP2010/058154 WO2010134466A1 (en) | 2009-05-21 | 2010-05-14 | Gas generant composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102428056A true CN102428056A (en) | 2012-04-25 |
| CN102428056B CN102428056B (en) | 2014-03-12 |
Family
ID=43126147
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201080021550.1A Active CN102428056B (en) | 2009-05-21 | 2010-05-14 | Gas generant composition |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20120055593A1 (en) |
| EP (1) | EP2444383B1 (en) |
| JP (1) | JP5441497B2 (en) |
| CN (1) | CN102428056B (en) |
| WO (1) | WO2010134466A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103443055A (en) * | 2011-03-31 | 2013-12-11 | 株式会社大赛璐 | Gas-forming agent composition |
| CN104411660A (en) * | 2012-10-18 | 2015-03-11 | 株式会社大赛璐 | Gas-generating-agent composition |
| CN109219539A (en) * | 2016-05-23 | 2019-01-15 | 均胜安全系统收购有限责任公司 | Gas-generating agent composition and its preparation and application |
| CN112010719A (en) * | 2019-05-29 | 2020-12-01 | 南京理工大学 | Aluminum-containing explosive and preparation method thereof |
| CN114505615A (en) * | 2022-02-28 | 2022-05-17 | 山东大学 | Flux-cored wire special for deep sea wet FCAW and preparation method |
| CN116249682A (en) * | 2020-10-01 | 2023-06-09 | 株式会社大赛璐 | Gas generating agent composition |
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| JP5785768B2 (en) | 2011-03-23 | 2015-09-30 | 株式会社ダイセル | Gas generant composition |
| JP6407505B2 (en) | 2012-10-18 | 2018-10-17 | 株式会社ダイセル | Gas generant composition |
| US9321956B2 (en) | 2012-11-28 | 2016-04-26 | Halliburton Energy Services, Inc. | Methods for hindering the settling of particulates in a subterranean formation |
| US9790774B2 (en) | 2014-01-02 | 2017-10-17 | Halliburton Energy Services, Inc. | Generating and maintaining conductivity of microfractures in tight formations by generating gas and heat |
| CN106458143B (en) | 2014-04-15 | 2019-09-13 | Tk控股公司 | The pedestrian's hood lifting device and seat belt pretensioner that silicone resin promotes |
| WO2017018996A1 (en) | 2015-07-24 | 2017-02-02 | Halliburton Energy Services, Inc. | Microbubbles for heat and/or gas generation in subterranean formations |
| CA2986545C (en) | 2015-07-24 | 2019-09-03 | Halliburton Energy Services, Inc. | Microbubbles for treatment chemical delivery in subterranean formations |
| JPWO2022102244A1 (en) | 2020-11-11 | 2022-05-19 | ||
| WO2023167222A1 (en) * | 2022-03-03 | 2023-09-07 | 株式会社ダイセル | Gas-generating agent composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103443055A (en) * | 2011-03-31 | 2013-12-11 | 株式会社大赛璐 | Gas-forming agent composition |
| CN103443055B (en) * | 2011-03-31 | 2015-11-25 | 株式会社大赛璐 | Gas generant composition |
| CN104411660A (en) * | 2012-10-18 | 2015-03-11 | 株式会社大赛璐 | Gas-generating-agent composition |
| CN109219539A (en) * | 2016-05-23 | 2019-01-15 | 均胜安全系统收购有限责任公司 | Gas-generating agent composition and its preparation and application |
| CN109219539B (en) * | 2016-05-23 | 2021-10-19 | 均胜安全系统收购有限责任公司 | Gas generating compositions and methods of making and using same |
| CN112010719A (en) * | 2019-05-29 | 2020-12-01 | 南京理工大学 | Aluminum-containing explosive and preparation method thereof |
| CN112010719B (en) * | 2019-05-29 | 2021-11-30 | 南京理工大学 | Aluminum-containing explosive and preparation method thereof |
| CN116249682A (en) * | 2020-10-01 | 2023-06-09 | 株式会社大赛璐 | Gas generating agent composition |
| CN114505615A (en) * | 2022-02-28 | 2022-05-17 | 山东大学 | Flux-cored wire special for deep sea wet FCAW and preparation method |
| CN114505615B (en) * | 2022-02-28 | 2023-01-17 | 山东大学 | Flux-cored wire special for deep sea wet FCAW and preparation method |
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| Publication number | Publication date |
|---|---|
| JP5441497B2 (en) | 2014-03-12 |
| EP2444383B1 (en) | 2019-08-07 |
| CN102428056B (en) | 2014-03-12 |
| JP2010269969A (en) | 2010-12-02 |
| WO2010134466A1 (en) | 2010-11-25 |
| EP2444383A4 (en) | 2014-01-01 |
| US20120055593A1 (en) | 2012-03-08 |
| EP2444383A1 (en) | 2012-04-25 |
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