EP0000270A1 - Procédé pour réparer des pièces métalliques à l'aide de compositions de résines durcissables - Google Patents
Procédé pour réparer des pièces métalliques à l'aide de compositions de résines durcissables Download PDFInfo
- Publication number
- EP0000270A1 EP0000270A1 EP78300073A EP78300073A EP0000270A1 EP 0000270 A1 EP0000270 A1 EP 0000270A1 EP 78300073 A EP78300073 A EP 78300073A EP 78300073 A EP78300073 A EP 78300073A EP 0000270 A1 EP0000270 A1 EP 0000270A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- parts
- ferrosilicon
- resin
- composition
- weight
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/10—Anti-corrosive paints containing metal dust
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/34—Filling pastes
Definitions
- This invention relates to hardenable resin compositions and especially, although not exclusively to hardenable resin compositions which require a separate catalyst or hardener to be added to them in order to produce a hardened resin.
- composition comprising a liquid polymerisable resin and ferrosilicon.
- the liquid resin is preferably a resin of one of the following types: epoxy, polyether, saturated polyester, polyol, isocyanate, polyamine, polyamide, polymercapton, silicone, unsaturated polyester, 'acrylate and methacrylate. More preferably the resin is an epoxy resin.
- the silicon content of the ferrosilicon is from 10 to 80, preferably 10 to 20 and more preferably about 15 parts by weight per 100 parts by weight ferrosilicon.
- ferrosilicon is present in an amount of from 250 to 350 parts by weight per 100 parts by weight of resin.
- the composition also includes silicon carbide in an amount of from 40 to 60 parts by weight per 250 parts by weight ferrosilicon.
- the composition also contains a silane as wetting agent in an amount of from 0.5 to 1.5 parts by weight per 100 parts by weight of resin.
- the present invention also provides a two component pack comprising a first component including a liquid polymerisable resin and a second component including a hardener for said resin, one or both of said first and second components also including ferrosilicon.
- Two component synthetic resin based compositions are widely used as repair materials throughout industry. Applications for these products include repairs to, and rebuilding of pumps, valves, engine blocks, cylinder liners, hydraulic rams, keyways, bearing housings, castings, shutes, hoppers, shafts, machine beds, condensers, sumps, transformers and many other applications.
- These synthetic resin based compositions normally consist of a base component and a solidifier component which when stored apart have a shelf life of months or even years.
- a chemical reaction occurs in the form of polymerisation yielding a product with totally different physical characteristics from the original components.
- This polymerisation reaction varies considerably, according to the chemical nature of the components involved.
- the reaction time for example can be as short as several seconds for certain cycloaliphatic Epoxy based compositions and as long as several days for compositions involving long chain polyamide resins.
- the physical properties of the end product from this polymerisation can vary from hard brittle polymers to extremely flexible synthetic rubbers.
- the resin types involved in formulating these compositions can be broadly classified into Epoxies, Polyurethanes, Unsaturated Polyesters, Silicones and Acrylics, although the present invention is not intended to be limited to any particular class of polymer or resin.
- Epoxy resin based compositions for example will always involve a molecule containing more than one ol Epoxy group (whether situated internally, terminally, or on cyclic structures).
- the solidifier component can vary however from simple amines such as diethylene triamine to complex polymercaptons. Similar variations can be described for polyurethanes, unsaturated polyesters, silicones and acrylics. With each type however two components are involved to produce the end polymer.
- the individual components possess none of these properties and could not be considered as repair compounds in the meaning of this particular patent.
- the resultant polymer however, after mixing, possesses all the above properties to varying degrees.
- the individual properties can be varied according to the nature and the type of resin employed. For example from Epoxy resin based compositions cured with amine solidifiers, polymers with outstanding hardness and f compressive strength can be produced. The same Epoxy resin based composition cured with a polyamide solidifier can produce a polymer with outstanding adhesion characteristics. By careful selection of base and solidifier components, polymers with outstanding adhesion, impact resistance, flexibility, flexural strength etc. can be produced.
- the components discussed in this patent application can be reinforced with numerous fillers. Fillers such as asbestine, talc and china clay can be incorporated to improve adhesion. Asbestos and fibrous type fillers jive improved impact resistance, whereas metallic fillers give rise to improved abrasion resistance and with careful selection of the filler involved a metallic filler can impart certain metallic characteristics to the polymer.
- liquid resin from the reaction process between 2.2 bis (4 hydroxyphenol) propane and ephichlorohydrin was blended with 100 mesh Iron powder in the ratio 100 parts liquid resin and 300 parts Iron powder by weight.
- the addition of 50 parts by weight of a liquid-Amidopolyamine resin gave a composition which polymerised over a period of 24 hours.
- the resultant polymer was exposed in the ASTM B117 Salt Spray and showed considerable rusting after'only 50 hours exposure.
- Iron powder in a two component synthetic resin based composition will also lower the chemical resistance of the resultant polymer.
- Metallic Iron is readily attacked by a wide variety of industrial chemicals including many acids and alkalis.
- Iron filled polymers as metal repair compositions therefore exhibit most of the disadvantages of the component they are repairing. Whilst this does not preclude their use as general.purpose repair compositions it does mean that the repair has a limited life. The abrasion and corrosion found in pumps for example will continue to attack the repaired area and frequent recoating will be necessary.
- Iron powder presents none of the above problems and of course produces a composition with similar characteristics to the repaired surface.
- the powders produced by the atomised process are generally spherical in shape, with the surface of the individual grains passivated by a thin oxide layer. This results in a powder with outstanding corrosion resistance.
- Granular Ferrosilicon however has a comparatively rough surface and the sharp corners and edges of this_-powder can give rise to corrosion under aggresive conditions.
- the Silicon content of the Ferrosilicon alloy can be varied according to the levels of Iron and Quartz used in the manufacturing process. In practice 15%, 45% and 75% Silicon levels are used and the conventional outlets for these alloys are as follows:-
- Electrode coatings - in coating Electrodes Silicon is used as a reducing agent, to bring the Silicon content into the weld. Ferrosilicon (with 45% Silicon) is widely used as the Silicon carrier in these coatings.
- Ferrosilicon with Silicon contents as high as 75% is used as an alloying material in Steel Mills and Foundries.
- the initial investigation consisted of the following work.
- the liquid resin from the reaction between 2.2 bis (4 hydroxyphenol) propane and epichlorohydrin was blended with 100 mesh Ferrosilicon in the ratio 100 parts resin to 300 parts Ferrosilicon by weight (Example II).
- the atomised grade of Ferrosilicon containing 15% Silicon being used.
- the addition of 50 parts by weight of a liquid amidopolyamine to this composition gave a product which polymerised in 24 hours , at 20°. Exposure of the resultant polymer in the ASTM B117 Salt Spray showed no evidence of corrosion after 50 hours.
- Example III the liquid resin from the reaction between 2.2 bis (4 hydroxyphenol) propane and epichlorohydrin was blended with Atomised Ferrosilicon (15% Silicon) in the ratio 100 parts liquid resin to 300 parts Ferrosilicon by weight. To this compositon 3.0 parts by weight of coagulated silicon dioxide from - the flame hydrolysis of Silicon Tetrachloride were added. This addition gave the composition a degree of thixotropy and produced a more stable blend of resin and Ferrosilicon. An addition of 20 parts by weight of an acid metasilicate of Magnesium improved this thixotropy still further and produced a composition (Example III) with excellent storage stability.
- Mill steel panels coated with all three examples given were tested on the Taber abrasion tester (manufactured by Taledyne Taber, New York). The Calibrade H10 wheels were used in this test and a 500 gram loading was applied.
- Example IV A comparison between this composition (Example. IV) and a composition where the 300 parts of 100 mesh Ferrosilicon were replaced weight for weight with Iron powder (Example V) gave the following results. After 100 hours exposure in the ASTM B117 Salt Spray the Ferrosilicon based composition (Example IV) was completely rust free whereas the Iron based composition (Example V) showed considerable rusting and corrosion.
- Example VI A further composition (Example VI) with an improved rate of polymerisation was examined as follows.
- the liquid resin from the reaction between 2.2 Bis (4 hydroxyphenol) propane and epichlorohydrin was blended with Atomised Ferrosilicon (15% Silicon) in the ratio 100 parts resin to 300 parts Ferrosilicon.
- 3.0 parts coagulated Silicon dioxide and 20.0 parts of an acid metasilicate of Magnesium were added to the above blend to produce a thixotropic composition (Example VI).
- This composition was polymerised by the addition of 25 parts of a liquid activated aromatic polyamine.
- the resultant polymer was hard after 1 hour at room temperature and on exposure in the ASTM B117 Salt Spray showed no sign of corrosion after 500 hours exposure.
- Example VIII the liquid resin from the reaction product between 2.2 bis (4 hydroxyphenol) propane and epichlorohydrin was blended with 100 mesh atomised Ferrosilicon in the ratio 100 parts resin to 250 parts Ferrosilicon by weight. 50 parts by weight of 150 mesh Silicon Carbide were added to this blend followed by 3.0 parts coagulated Silicon Dioxide and 20.0 parts of an acid metasilicate of Magnesium.
- the resulting composition was polymerised with 25 parts of a liquid activated aromatic amine to produce a polymer with outstanding abrasion resistance.
- Example III Composition-as given in Example III 0.0770 grams Composition as given in Example VIII - 0.0160 grams
- the above figures are expressed as weight of polymer removed after 500 cycles and clearly show the superior abrasion resistance of the polymer given in Example VIII.
- This polymer still exhibited many of the advantages of earlier examples, in that the material was strongly magnetic and could be drilled and tapped like conventional metal.
- the machining characteristics of this polymer were inferior to Examples II to VII however, the presence of Silicon Carbide producing excessive wear on any tool tips used in the machining process.
- Example IX the liquid resin from the reaction between 2.2 bis (4 hydroxyphenol) propane and epichlorohydrin was blended with 100 mesh atomised Ferrosilicon. in the ratio 100 parts resin to 300 parts Ferrosilicon. 3.0 parts coagulated Silicon dioxide and 20.0 parts by weight of an acid metasilicate of Magnesium were added to the above blend followed by 1.0 parts of gamma Glycidoxypropyltrimethoxyoilane.
- Example IX The above composition (Example IX) was polymerised using 25.0 parts of a liquid activated aromatic polyamine and produced a polymer with outstanding adhesion to metal surfaces.
- the contaminated steel substrates were obtained by dipping the steel test pieces in mineral oil and water respectively at 20°C and allowing the test piece to stand for 30 minutes prior to the application of the polymer under test.
- Example IX The work outlined in Example I to IX has involved the evaluation of Atomised Ferrosilicon in a liquid resin from the reaction between 2.2 bis (4 hydroxyphenol) propane and epichlorohydrin.
- Examples X and XI the use of Ferrosilicon in alternative polymer compositions was investigated.
- 100 parts of a liquid branched polyalcohol with a hydroxyl content of 5% were blended with 300 parts of 100 mesh atomised Ferrosilicon. 3.0 parts coagulated silicon dioxide and 20.0 parts of an acid metasilicate of magnesium were added to the above blend followed by 10.0 parts of a crystalline aluminosilicate with a cavity diameter of 11.4A.
- This composition (Example X) was polymerised by the addition of 40 parts of diphenyl methane 4-4 diisocyanate. The resulting polymer was exposed in the ASTM B117 Salt Spray and showed no sign of corrosion after 500 hours exposure. The formulation was strongly magnetic and could be machined, tapped and drilled with ease. Comparison between this composition and a similar composition based on Iron powder showed almost identical machining properties. The latter material showed considerable corrosion in the ASTM B117 Salt Spray after only 100 hours exposure however.
- Example XI an unsaturated polyester resin containing 35% styrene by weight was blended with 100 mesh atomised Ferrosilicon (15% Silicon) in the ratio 10.0 parts resin to 300 parts Ferrosilicon by weight. 3.0 parts coagulated silicon dioxide and 20.0 parts-of an-acid metasilicate of magnesium'were added to this blend to produce a thixotropic composition (Example XI).
- the addition of 10.0 parts of a 50% dispersion of Benzoyl Peroxide in dibutyl phthalate plasticiser gave rise to rapid polymerisation and a hard polymer was produced within 20 minutes of the peroxide addition. This polymer was exposed in the ASTM B117 Salt Spray and showed no signs of corrosion after 500 hours exposure. A similar composition on Iron powder showed extensive corrosion in the same test after only 100 hours exposure.
- Example XI The polymer from Example XI was strongly magnetic and could be machined, drilled and-tapped like conventional metal.
- the storage stability of this composition was considerably better than that of a similar composition based on Iron powder. After 6 months storage at 20°C the Base component was still in good condition whereas it is a known fact that unsaturated polyester resins blended with Iron powder have a limited storage life of 1 - 2 months. This improved storage stability is obviously due to the reduced reactivity and passivation of the Ferrosilicon powder after the atomisation process.
- liquid resin from the reaction between 2.2 bis (4 hydrosyphenol) propane and epichlorohydrin was blended with an acid metasilicate of magnesium in the ratio 100 parts resin to 20 parts metasilicate by weight. 3.0 parts of coagulated silicon dioxide were added to the above blend to produce a semi thixotropic composition.
- Example XII (15% Silicon) was strongly magnetic whereas Example XIII (45% Silicon) was only weakly magnetic and Example XIV (75% Silicon) showed no evidence of magnetism.
- the abrasion resistance of all-three formulations was of a similar order and was consistently higher than the abrasion resistance of a composition based on Iron powder as in Example I.
- the liquid resin from the reaction between 2.2 bis (4 hydroxy phenol) propane and epichlorohydrin was mixed with 100 mesh atomised Ferrosilicon (15% Silicon) in the ratio 100 parts Resin to 300 parts Ferrosilicon by weight. 3.0 parts of coagulated Silicon dioxide and 20.0 parts of an acid metasilicate of magnesium were added to the above blend to produce a thixotropic composition (Example XV).
- the composition was polymerised by the addition of 25 parts of a liquid activated aromatic amine. This polymer was compared with a similar composition where the atomised Ferrosilicon was replaced on a weight for weight basis with 100 mesh Angular Ferrosilicon (15% Silicon).
- the level of Silicon in the Ferrosilicon alloy can be varied considerably although optimum results are obtained with a composition based on 15% Silicon, 85% Iron.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB2632777 | 1977-06-23 | ||
GB26327/77A GB1600612A (en) | 1977-06-23 | 1977-06-23 | Repairing metal parts |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0000270A1 true EP0000270A1 (fr) | 1979-01-10 |
EP0000270B1 EP0000270B1 (fr) | 1981-12-09 |
Family
ID=10241925
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP78300073A Expired EP0000270B1 (fr) | 1977-06-23 | 1978-06-23 | Procédé pour réparer des pièces métalliques à l'aide de compositions de résines durcissables |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0000270B1 (fr) |
DE (1) | DE2861431D1 (fr) |
GB (1) | GB1600612A (fr) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2143533A (en) * | 1983-07-18 | 1985-02-13 | Grace W R & Co | Weldable sealants for metals and their use |
CN112295877A (zh) * | 2020-10-23 | 2021-02-02 | 云南华电鲁地拉水电有限公司 | 一种防止水轮机过流部件局部汽蚀的方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR648615A (fr) * | 1928-02-10 | 1928-12-12 | Peinture protectrice | |
NL6905886A (en) * | 1969-04-16 | 1970-10-20 | Silicon carbide filler in hardenable abrasion - -resistant casting resins | |
GB1313293A (en) * | 1969-04-16 | 1973-04-11 | Albright & Wilson | Filled polymer compositions |
JPS4997098A (fr) * | 1972-12-19 | 1974-09-13 |
-
1977
- 1977-06-23 GB GB26327/77A patent/GB1600612A/en not_active Expired
-
1978
- 1978-06-23 DE DE7878300073T patent/DE2861431D1/de not_active Expired
- 1978-06-23 EP EP78300073A patent/EP0000270B1/fr not_active Expired
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR648615A (fr) * | 1928-02-10 | 1928-12-12 | Peinture protectrice | |
NL6905886A (en) * | 1969-04-16 | 1970-10-20 | Silicon carbide filler in hardenable abrasion - -resistant casting resins | |
GB1313293A (en) * | 1969-04-16 | 1973-04-11 | Albright & Wilson | Filled polymer compositions |
JPS4997098A (fr) * | 1972-12-19 | 1974-09-13 |
Non-Patent Citations (1)
Title |
---|
CHEMICAL ABSTRACTS 82, 60138d (1975) & JP-A-49 097098 (NITTO ELECTRIC) * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2143533A (en) * | 1983-07-18 | 1985-02-13 | Grace W R & Co | Weldable sealants for metals and their use |
US4559373A (en) * | 1983-07-18 | 1985-12-17 | W. R. Grace & Co. | Weldable sealants for metal and method of use |
CN112295877A (zh) * | 2020-10-23 | 2021-02-02 | 云南华电鲁地拉水电有限公司 | 一种防止水轮机过流部件局部汽蚀的方法 |
Also Published As
Publication number | Publication date |
---|---|
DE2861431D1 (en) | 1982-02-04 |
EP0000270B1 (fr) | 1981-12-09 |
GB1600612A (en) | 1981-10-21 |
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