EP0299950B1 - Halogen-containing fillers for abrasive articles, method for the production of these fillers and abrasive articles containing them - Google Patents

Halogen-containing fillers for abrasive articles, method for the production of these fillers and abrasive articles containing them Download PDF

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Publication number
EP0299950B1
EP0299950B1 EP88890179A EP88890179A EP0299950B1 EP 0299950 B1 EP0299950 B1 EP 0299950B1 EP 88890179 A EP88890179 A EP 88890179A EP 88890179 A EP88890179 A EP 88890179A EP 0299950 B1 EP0299950 B1 EP 0299950B1
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EP
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Prior art keywords
halogen
fluorine compound
oxygen acid
ammonium
filler
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EP88890179A
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German (de)
French (fr)
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EP0299950A1 (en
Inventor
Lothar Dr. Buxbaum
Helmut Dipl.-Ing. Stessel
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Chemson Polymer Additive AG
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BBU Chemie GmbH
Chemson Polymer Additive AG
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
    • B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
    • B24D3/34—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents characterised by additives enhancing special physical properties, e.g. wear resistance, electric conductivity, self-cleaning properties
    • B24D3/346—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents characterised by additives enhancing special physical properties, e.g. wear resistance, electric conductivity, self-cleaning properties utilised during polishing, or grinding operation

Definitions

  • the invention relates to halogen-containing fillers for grinding wheels, in particular for grinding or cutting discs, a process for producing these fillers and grinding wheels containing them.
  • Abrasives e.g. Cutting discs essentially consist of three components, namely the abrasive, granular abrasive, a binder, and fillers. So-called abrasive fillers have become known for absorbing and dissipating the frictional heat generated during the grinding process, for reducing the friction between the grinding body and the workpiece and for forming protective films on the abrasive grain, workpiece and chips.
  • halides previously used as grinding fillers are always somewhat hygroscopic. This leads, among other things, to e.g. react strongly with the resole resins (phenolic resins) usually used as binders, so that the abrasives have lower and uneven strength. There is also a greasy body surface that affects grinding performance, as well as signs of corrosion on machines and workpieces.
  • the properties of the halogen-containing abrasive fillers according to AT-B-372894, EP-B-8697 and / or DE-A-3441596 can be improved substantially if they are combined with at least one fluorine compound, in particular uses at least one fluoride, and / or at least one salt of an oxygen acid of nitrogen, phosphorus and / or sulfur.
  • the various oxygen acids of nitrogen, phosphorus and sulfur are e.g. in Hollemann-Wiberg, Textbook of inorganic chemistry, 81st to 90th edition, pages 401 to 413, 444 to 461 and 328 to 350, to which reference is made as a disclosure.
  • the cations of the fluorine compounds and oxygen acid salts are selected from at least one component of the group containing ammonium, the alkali and alkaline earth metals, Al, B, Co, Cu, Fe, Mn, Ni, Sn, Ti and Zn, where nitrates, phosphates and sulfates, for example Ca (NO3) 2, may be mentioned as the simplest examples of the oxygen salts mentioned.
  • the at least one fluorine compound is selected from the group comprising fluorides, fluorosulfates, fluorophosphates, fluoroaluminates and fluoroborates, with fluorides being preferred.
  • the proportion of additional either a) fluorine compound, or b) oxygen acid salt or c) combination of fluorine compound and oxygen acid salt is in each case 1 to 40% by mass, based on the halogen-containing filler, a proportion of 3 to 20% by mass being preferred .
  • the fluorine compounds in particular fluorides, and / or the salts of the oxygen acids of nitrogen, phosphorus and / or sulfur, can be the known halogen-containing abrasive fillers which - e.g. if they are complex salts - may also contain an excess of alkali chloride (e.g. 15 mol%), e.g. described in EP-B-8697, simply added;
  • alkali chloride e.g. 15 mol
  • the addition is advantageously carried out during the production of the halogen-containing fillers themselves, e.g. these additives are added to the starting products either in the melt or in solution and then the resulting composition is processed into a fine powder in a known manner.
  • the additives according to the invention can be used individually or as a mixture of several of these substances.
  • the pH can be adjusted so that a largely neutral product is produced, e.g. in the case of complex salts in amounts of 2 to 20% by mass, based on the complex salt.
  • Abrasive bodies according to the invention in particular grinding wheels, contain an abrasive, granular abrasive, a binder, phenolic resins in particular being common as binders, and a filler according to the invention, if appropriate, in addition to other fillers.
  • the proportion of the filler according to the invention, in particular based on a metal complex halide, is advantageously at least 5% by mass, based on the total filler.
  • organic halogen compounds in particular chlorine and / or bromine compounds, can be added.
  • the grinding wheels according to the invention are manufactured in a known manner - e.g. by mixing the components, press forms and hardening - and show good cutting qualities (white cut) and high cutting performance. Due to the almost gone hygroscopicity of the filler, the grinding wheels harden more evenly, there are fewer wheel breaks. When stored in a humid climate, the grinding wheels remain superficially dry.
  • the complex salt obtained whose approach to the production of K4MnCl6 (or K2MnCl4 ⁇ 2 KCl) is based, consists of at least 50% of this compound; there are other complex compounds, especially K3MnCl5, K2MnCl4 and KMnCl3, and free potassium chloride. This is a phenomenon that i.a. is also present in the complexes of the prior art, since it is typical of such compounds.
  • the water uptake was determined as follows: The samples were sieved and 2 g of the fraction ⁇ 125 ⁇ each were spread uniformly on a crystallizing dish. The dishes were placed in a 65% rel. Stored in humidity and determined the respective weight gain after 100 hours.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Polishing Bodies And Polishing Tools (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

Proposed is a halogen-containing filler for abrasive bodies on the basis of at least one metal halide or metal complex salt of the formula AxMeyIIMezIIIHalE.nBfCgHale.mH2O.oNH3 wherein A: is an alkali metal or ammonium, x: a number of 0 to 10, MeII: Mn, C, Mg, Zn, Sn, Cu, Co or Ni, y: a number of 0 to 2, MeIII: Al, B or Ti, z: a number of 0 to 2, Hal: a halogen, E: a number of 1 to 10, n: a number of 0 to 10, B: an alkali metal or ammonium, f: a number of 0 to 1, C: Ca, Mg, Zn, Sn or Mn, g: a number of 0 to 1, e: a number of 1 to 2, m: a number of 0 to 10 and o: a number of 0 to 10, and/or at least one alkali chloroferrate (II,III) of the formula AxFey++Fez+++Clx+2y+3z wherein A represents an alkali metal or ammonium, x stands for a number of 1 to 10, y is a number of zero to 1 and z is a number from zero to 1 and y and z are not simultaneously zero, the ferrate preferably being formed in combination with a basic inorganic compound such as zinc oxide, potassium carbonate or sodium sulfide, and/or at least one mixture of a basic aluminum chloride with NaCl and/or KCl, which is characterized above all in that it contains at least one fluorine compound, in particular at least one fluoride, and/or at least one salt of an oxygen acid of nitrogen, phosphorus and/or sulfur; an abrasive body, in particlar for metals, which contains this filler, said body containing an abrasive, a binder as well as said active, halogen-containing filler, optionally in addition to other fillers, as well as a process for the production of said filler.

Description

Die Erfindung betrifft halogenhaltige Füllstoffe für Schleifkörper, insbesondere für Schleif- oder Trennscheiben, ein Verfahren zur Herstellung dieser Füllstoffe sowie diese enthaltende Schleifkörper.The invention relates to halogen-containing fillers for grinding wheels, in particular for grinding or cutting discs, a process for producing these fillers and grinding wheels containing them.

Schleifkörper, z.B. Trennscheiben, bestehen im wesentlichen aus drei Komponenten, nämlich dem abrasiven, körnigen Schleifmittel, einem Bindemittel, und Füllstoffen. Zur Aufnahme und Abführung der beim Schleifvorgang entstehenden Reibungswärme, zur Herabsetzung der Reibung zwischen Schleifkörper und Werkstück und zur Bildung von Schutzfilmen auf Schleifkorn, Werkstück und Spänen sind sogenannte schleifaktive Füllstoffe bekannt geworden.Abrasives, e.g. Cutting discs essentially consist of three components, namely the abrasive, granular abrasive, a binder, and fillers. So-called abrasive fillers have become known for absorbing and dissipating the frictional heat generated during the grinding process, for reducing the friction between the grinding body and the workpiece and for forming protective films on the abrasive grain, workpiece and chips.

Unter den zahlreichen als schleifaktive Füllstoffe eingesetzten Verbindungen sind Metallhalogenide und komplexe (mehrere Metalle enthaltende) Metallhalogenide besonders verbreitet. So betrifft z.B. die AT-B-372894 derartige Halogenide bzw. komplexe Halogenide der Formel

Figure imgb0001

wobei

A
ein Alkalimetall oder Ammonium,
x
eine Zahl von 0 bis 10.
MeII
Mn, Ca, Mg, Zn, Sn, Cu, Co oder Ni,
y
eine Zhal von 0 bis 2,
MeIII
Al, B oder Ti ist,
z
eine Zahl von 0 bis 2,
Hal
ein Halogen darstellt,
E
eine Zahl von 1 bis 10 ist;
n
eine Zahl von 0 bis 10.
B
ein Alkalimetall oder Ammonium ist.
f
eine Zahl von 0 bis 1 ist.
C
Ca, Mg, Zn, Sn oder Mn,
g
eine Zahl von 0 bis 1 ist.
e
eine Zahl von 1 bis 2 ist.
m
eine Zahl von 0 bis 10 und
o
eine Zahl von 0 bis 10 ist,


wobei als Beispiele Manganchloride, komplexe Manganchloride und komplexe Zinnchloride, die jeweils außer Mangan bzw. Zinn noch NH₄ oder K enthalten, angeführt sind. In der US-A-2216135 werden für diesen Zweck wasserfreie, wasserlösliche, nicht oxydierende anorganische Alkali- oder Erdalkalisalze mit Schmelzpunkten im Bereich von 700 bis 1200°C vorgeschlagen, wobei als Halogenide Chloride und Bromide genannt sind. Die EP-B-8697 beschreibt in diesem Zusammenhang Alkalichloroferrate (II, III) der Formel
Figure imgb0002
wobei A ein Alkalimetall oder Ammonium ist, x eine Zahl von 1 bis 10, y eine Zahl von Null bis 1 und z eine Zahl von Null bis 1 ist und y und z nicht gleichzeitig Null sind, wobei das Ferrat vorzugsweise in Kombination mit einer basischen anorganischen Verbindung, z.B. Zinkoxid, Kaliumcarbonat oder Natriumsulfid gebildet ist, die auch im Gemisch mit KCl oder NaCl einsetzbar sind, und die DE-A-3441596 beschreibt Gemische aus basischem Aluminiumchlorid und KCl und/oder NaCl.Among the numerous compounds used as grinding-active fillers, metal halides and complex (containing several metals) metal halides are particularly widespread. For example, AT-B-372894 relates to such halides or complex halides of the formula
Figure imgb0001
in which
A
an alkali metal or ammonium,
x
a number from 0 to 10.
Me II
Mn, Ca, Mg, Zn, Sn, Cu, Co or Ni,
y
a zhal from 0 to 2,
Me III
Is Al, B or Ti,
e.g.
a number from 0 to 2,
Hal
represents a halogen,
E
is a number from 1 to 10;
n
a number from 0 to 10.
B
is an alkali metal or ammonium.
f
is a number from 0 to 1.
C.
Ca, Mg, Zn, Sn or Mn,
G
is a number from 0 to 1.
e
is a number from 1 to 2.
m
a number from 0 to 10 and
O
is a number from 0 to 10,


with examples being manganese chlorides, complex manganese chlorides and complex tin chlorides, each of which contains NH₄ or K in addition to manganese or tin. For this purpose, US-A-2216135 describes anhydrous, water-soluble, non-oxidizing inorganic Alkali or alkaline earth metal salts with melting points in the range from 700 to 1200 ° C. are proposed, chlorides and bromides being mentioned as halides. In this context, EP-B-8697 describes alkali chloroferrates (II, III) of the formula
Figure imgb0002
where A is an alkali metal or ammonium, x is a number from 1 to 10, y is a number from zero to 1 and z is a number from zero to 1 and y and z are not simultaneously zero, the ferrate preferably in combination with a basic one inorganic compound, for example zinc oxide, potassium carbonate or sodium sulfide, which can also be used in a mixture with KCl or NaCl, and DE-A-3441596 describes mixtures of basic aluminum chloride and KCl and / or NaCl.

Ein wesentlicher Nachteil der bisher als schleifaktive Füllstoffe eingesetzten Halogenide ist der Umstand, daß sie stets in gewissem Maße hygroskopisch sind. Dies führt unter anderem dazu, daß sie z.B. mit den üblicherweise als Bindemittel eingesetzten Resolharzen (Phenolharzen) stark reagieren, so daß die Schleifkörper geringere und ungleichmäßige Festigkeit aufweisen. Weiterhin ergeben sich eine schmierige Körperoberfläche, die die Schleifleistung beeinträchtigt, sowie Korrosionserscheinungen an Maschinen und Werkstücken.A major disadvantage of the halides previously used as grinding fillers is the fact that they are always somewhat hygroscopic. This leads, among other things, to e.g. react strongly with the resole resins (phenolic resins) usually used as binders, so that the abrasives have lower and uneven strength. There is also a greasy body surface that affects grinding performance, as well as signs of corrosion on machines and workpieces.

Dies war bereits erkannt worden und in der AT-B-372894 ist angegeben, daß die dort vorgeschlagenen besonderen Metallhalogenide eine sehr geringe Hygroskopizität aufweisen sollen.This had already been recognized and AT-B-372894 states that the particular metal halides proposed there should have a very low hygroscopicity.

Nunmehr wurde überraschenderweise gefunden, daß man die Eingenschaften der halogenhaltigen schleifaktiven Füllstoffe gemäß der AT-B-372894, der EP-B-8697 und/oder der DE-A-3441596 weigehend verbessern kann, wenn man sie zusammen mit mindestens einer Fluorverbindung, insbesondere mindestens einem Fluorid, und/oder mindestens einem Salz einer Sauerstoffsäure des Stickstoffs, Phosphors und/oder Schwefels einsetzt.It has now surprisingly been found that the properties of the halogen-containing abrasive fillers according to AT-B-372894, EP-B-8697 and / or DE-A-3441596 can be improved substantially if they are combined with at least one fluorine compound, in particular uses at least one fluoride, and / or at least one salt of an oxygen acid of nitrogen, phosphorus and / or sulfur.

Dementsprechend ist der erfindungsgemäße halogenhaltige Füllstoff für Schleifkörper, auf Basis mindestens eines Metallhalogenids bzw. Metallkomplexsalzes der Formel

Figure imgb0003

wobei

A
ein Alkalimetall oder Ammonium,
x
eine Zahl von 0 bis 10,
MeII
Mn, Ca, Mg, Zn, Sn, Cu, Co oder Ni,
y
eine Zahl von 0 bis 2,
MeIII
Al, B oder Ti ist,
z
eine Zahl von 0 bis 2,
Hal
ein Halogen darstellt,
E
eine Zahl von 1 bis 10 ist;
n
eine Zahl von 0 bis 10,
B
ein Alkalimetall oder Ammonium ist,
f
eine Zahl von 0 bis 1 ist,
C
Ca, Mg, Zn, Sn oder Mn,
g
eine Zahl von 0 bis 1 ist,
e
eine Zahl von 1 bis 2 ist,
m
eine Zahl von 0 bis 10 und
o
eine Zahl von 0 bis 10 ist,


und/oder mindestens eines Alkalichloroferrats (II, III) der Formel
Figure imgb0004
wobei A ein Alkalimetall oder Ammonium ist, x eine Zahl von 1 bis 10, y eine Zahl von Null bis 1 und z eine Zahl von Null bis 1 ist und y und z nicht gleichzeitig Null sind, wobei das Ferrat vorzugsweise in Kombination mit einer basischen anorganischen Verbindung, z.B. Zinkoxid, Kaliumcarbonat oder Natriumsulfid gebildet ist, und/oder mindestens eines Gemisches aus einem basischen Aluminiumchlorid mit NaCl und/oder KCl, dadurch gekennzeichnet, daß er zusätzlich entweder a) mindestens eine Fluorverbindung, oder b) mindestens ein Salz einer Sauerstoffsäure aus der Elementengruppe, die Stickstoff, Phosphor und Schwefel enthält, oder c) mindestens eine Fluorverbindung in Kombination mit mindestens einem unter b) genannten Sauerstoffsäuresalz umfaßt.Accordingly, the halogen-containing filler according to the invention for abrasive articles is based on at least one metal halide or metal complex salt of the formula
Figure imgb0003
in which
A
an alkali metal or ammonium,
x
a number from 0 to 10,
Me II
Mn, Ca, Mg, Zn, Sn, Cu, Co or Ni,
y
a number from 0 to 2,
Me III
Is Al, B or Ti,
e.g.
a number from 0 to 2,
Hal
represents a halogen,
E
is a number from 1 to 10;
n
a number from 0 to 10,
B
is an alkali metal or ammonium,
f
is a number from 0 to 1,
C.
Ca, Mg, Zn, Sn or Mn,
G
is a number from 0 to 1,
e
is a number from 1 to 2,
m
a number from 0 to 10 and
O
is a number from 0 to 10,


and / or at least one alkali chloroferrate (II, III) of the formula
Figure imgb0004
where A is an alkali metal or ammonium, x is a number from 1 to 10, y is a number from 0 to 1 and z is a number from 0 to 1 and y and z are not simultaneously zero, the ferrate preferably in combination with a basic one inorganic compound, for example zinc oxide, potassium carbonate or sodium sulfide, and / or at least one mixture of a basic aluminum chloride with NaCl and / or KCl, characterized in that it additionally contains either a) at least one fluorine compound or b) at least one salt of an oxygen acid from the group of elements which contains nitrogen, phosphorus and sulfur, or c) comprises at least one fluorine compound in combination with at least one oxygen acid salt mentioned under b).

Die verschiedenen Sauerstoffsäuren des Stickstoffs, des Phosphors und des Schwefels sind z.B. in Hollemann-Wiberg, Lehrbuch der anorganischen Chemie, 81. bis 90. Auflage, Seiten 401 bis 413, 444 bis 461 und 328 bis 350 beschrieben, worauf als Offenbarung Bezug genommen wird.The various oxygen acids of nitrogen, phosphorus and sulfur are e.g. in Hollemann-Wiberg, Textbook of inorganic chemistry, 81st to 90th edition, pages 401 to 413, 444 to 461 and 328 to 350, to which reference is made as a disclosure.

Erfindungsgemäß sind die Kationen der Fluorverbindungen und Sauerstoffsäuresalze ausgewählt aus mindestens einem Bestandteil der Gruppe enthaltend Ammonium, die Alkali- und Erdalkalimetalle, Al, B, Co, Cu, Fe, Mn, Ni, Sn, Ti und Zn, wobei als einfachste Beispiele für die genannten Sauerstoffsäuresalze Nitrate, Phosphate und Sulfate genannt werden, z.B. Ca(NO₃)₂.According to the invention, the cations of the fluorine compounds and oxygen acid salts are selected from at least one component of the group containing ammonium, the alkali and alkaline earth metals, Al, B, Co, Cu, Fe, Mn, Ni, Sn, Ti and Zn, where nitrates, phosphates and sulfates, for example Ca (NO₃) ₂, may be mentioned as the simplest examples of the oxygen salts mentioned.

Weiterhin ist erfindungsgemäß die mindestens eine Fluorverbindung ausgewählt aus der Gruppe enthaltend Fluoride, Fluorosulfate, Fluorophosphate, Fluoroaluminate und Fluoroborate, wobei Fluoride bevorzugt sind.Furthermore, according to the invention the at least one fluorine compound is selected from the group comprising fluorides, fluorosulfates, fluorophosphates, fluoroaluminates and fluoroborates, with fluorides being preferred.

Endlich beträgt erfindungsgemäß der Anteil an zusätzlicher entweder a) Fluorverbindung, oder b) Sauerstoffsäuresalz oder c) Kombination aus Fluorverbindung und Sauerstoffsäuresalz jeweils 1 bis 40 Masse-%, bezogen auf den halogenhaltigen Füllstoff, wobei ein Anteil von 3 bis 20 Masse-% bevorzugt ist.Finally, according to the invention, the proportion of additional either a) fluorine compound, or b) oxygen acid salt or c) combination of fluorine compound and oxygen acid salt is in each case 1 to 40% by mass, based on the halogen-containing filler, a proportion of 3 to 20% by mass being preferred .

Die Fluorverbindvngen, insbesondere Fluoride, und/oder die Salze der Sauerstoffsäuren des Stickstoffs, Phosphors und/oder Schwefels, können den bekannten halogenhaltigen schleifaktiven Füllstoffen, die  ―  z.B. wenn sie Komplexsalze sind  ―  auch einen Überschuß an Alkalichlorid (z.B. 15 Mol-%) enthalten können, wie z.B. in der EP-B-8697 beschrieben, einfach zugegeben werden; günstig erfolgt die Zugabe jedoch bei der Herstellung der halogenhaltigen Füllstoffe selbst, z.B. werden diese Zusätze entweder in der Schmelze oder in Lösung den Ausgangsprodukten zugesetzt und dann die so entstandene Komposition in bekannter Weise zu einem feinen Pulver verarbeitet.The fluorine compounds, in particular fluorides, and / or the salts of the oxygen acids of nitrogen, phosphorus and / or sulfur, can be the known halogen-containing abrasive fillers which - e.g. if they are complex salts - may also contain an excess of alkali chloride (e.g. 15 mol%), e.g. described in EP-B-8697, simply added; However, the addition is advantageously carried out during the production of the halogen-containing fillers themselves, e.g. these additives are added to the starting products either in the melt or in solution and then the resulting composition is processed into a fine powder in a known manner.

Die erfindungsgemäßen Zusätze können einzeln oder als ein Gemisch mehrerer dieser Substanzen zum Einsatz kommen.The additives according to the invention can be used individually or as a mixture of several of these substances.

Durch den Zusatz basischer anorganischer Verbindungen wie z.B. Zinkoxid, Alkalicarbonat oder Natriumsulfid kann der pH-Wert so eingestellt werden, daß ein weitgehend neutrales Produkt entsteht, z.B. bei Komplexsalzen in Mengen von 2 bis 20 Masse-%, bezogen auf das Komplexsalz.By adding basic inorganic compounds such as Zinc oxide, alkali carbonate or sodium sulfide, the pH can be adjusted so that a largely neutral product is produced, e.g. in the case of complex salts in amounts of 2 to 20% by mass, based on the complex salt.

Erfindungsgemäße Schleifkörper, insbesondere Schleifscheiben, enthalten ein abrasives, körniges Schleifmittel, ein Bindemittel, wobei vor allem Phenolharze als Bindemittel üblich sind, und einen erfindungsgemäßen Füllstoffgegebenenfalls neben anderen Füllstoffen.Abrasive bodies according to the invention, in particular grinding wheels, contain an abrasive, granular abrasive, a binder, phenolic resins in particular being common as binders, and a filler according to the invention, if appropriate, in addition to other fillers.

Vorteilhaft beträgt dabei der Anteil des erfindungsgemäßen Füllstoffs, insbesondere auf Basis eines Metall-Komplexhalogenids, mindestens 5 Masse-%, bezogen auf den Gesamtfüllstoff.The proportion of the filler according to the invention, in particular based on a metal complex halide, is advantageously at least 5% by mass, based on the total filler.

Dem erfindungsgemäßen Füllstoff können neben anorganischen Halogenverbindungen, wie z.B. Alkali- und/oder Erdalkalichloriden, auch organische Halogenverbindungen, insbesondere Chlor- und/oder Bromverbindungen, zugesetzt werden.In addition to inorganic halogen compounds, such as e.g. Alkali and / or alkaline earth chlorides, also organic halogen compounds, in particular chlorine and / or bromine compounds, can be added.

Die Verwendung von K- und Na-Sulfat und -Pyrophosphat sowie von Magnesiumsulfat als solchem als Zusatz zu Schleifkörpern ist aus der US-A-2216135 bekannt, jedoch nicht in Kombination mit halogenhaltigen, schleifaktiven Füllstoffen.The use of K and Na sulfate and pyrophosphate as well as magnesium sulfate as such as an additive to grinding wheels is known from US Pat. No. 2,216,135, but not in combination with halogen-containing, grinding-active fillers.

Die erfindungsgemäben Schleifscheiben werden in bekannter Weise hergestellt  ―  z.B. durch Vermischen der Komponenten, Preßformen und Härten  ―  und zeigen gute Schnittqualitäten (weiber Schnitt) und hohe Trennleistungen. Wegen der fast verschwundenen Hygroskopizität des Füllstoffes härten die Schleifscheiben gleichmäßiger aus, es gibt weniger Scheibenbrüche. Bei lagerung in feuchtem Klima bleiben die Schleifscheiben oberflächlich trocken.The grinding wheels according to the invention are manufactured in a known manner - e.g. by mixing the components, press forms and hardening - and show good cutting qualities (white cut) and high cutting performance. Due to the almost gone hygroscopicity of the filler, the grinding wheels harden more evenly, there are fewer wheel breaks. When stored in a humid climate, the grinding wheels remain superficially dry.

Im folgenden wird die Erfindung anhand einiger Beispiele, die die erfindungsgemäße Modifizierung von halogenhaltigem Metallkomplexsalzen beschreiben, näher erläutert.The invention is explained in more detail below with the aid of some examples which describe the modification of halogen-containing metal complex salts according to the invention.

Beispiel 1:Example 1: 1.1) Herstellung des Komplexsalzes:1.1) Preparation of the complex salt:

738,4 g KCl und 490 g MnCl₂-4 H₂O wurden im Graphittiegel bei 700°C geschmolzen. Nach dem Aufhören der Gasblasenentwicklung wurde die Schmelze noch 30 min bei 700°C gehalten, dann in eine Gußeisenform gegossen und nach einstündigem Abkühlen die erhaltene Festsubstanz im Backenbrecher vorgebrochen und anschließend vermahlen.738.4 g KCl and 490 g MnCl₂-4 H₂O were melted in the graphite crucible at 700 ° C. After the gas bubble development had ceased, the melt was kept at 700 ° C. for a further 30 minutes, then poured into a cast iron mold and, after cooling for one hour, the solid substance obtained was broken up in the jaw crusher and then ground.

Das erhaltene Komplexsalz, dessen Ansatz auf die Herstellung von K₄MnCl₆ (bzw. K₂MnCl₄  ·  2 KCl) abgestellt ist, besteht zu mindestens 50 % aus dieser Verbindung; daneben liegen andere Komplexverbindungen, vor allem K₃MnCl₅, K₂MnCl₄ sowie KMnCl₃, und freies Kaliumchlorid vor. Dies ist eine Erscheinung, die u.a. auch bei den Komplexen des Standes der Technik vorliegt, da sie typisch für derartige Verbindungen ist.The complex salt obtained, whose approach to the production of K₄MnCl₆ (or K₂MnCl₄ · 2 KCl) is based, consists of at least 50% of this compound; there are other complex compounds, especially K₃MnCl₅, K₂MnCl₄ and KMnCl₃, and free potassium chloride. This is a phenomenon that i.a. is also present in the complexes of the prior art, since it is typical of such compounds.

1.2) Modifizierung des Komplexsalzes:1.2) Modification of the complex salt:

Dem Ansatz 1.1) wurden vor dem Aufschmelzen jeweils 10 Masse-% Modifizierungsmittel, bezogen auf den Ansatz 1.1), zugesetzt und der Ansatz wie unter 1.1) angegeben verarbeitet.Before the melting, 10% by mass of modifier, based on batch 1.1), was added to batch 1.1) and the batch was processed as indicated under 1.1).

Die erhaltenen Ergebnisse sind in der folgenden Tabelle zusammengefaßt:

Figure imgb0005
The results obtained are summarized in the following table:
Figure imgb0005

Beispiel 2:Example 2: 2.1) Herstellung des Komplexsalzes:2.1) Preparation of the complex salt:

340,8 g ZnCl₂ wurden mit 745,5 g KCl vermischt und im Graphittiegel bei 700°C geschmolzen. Die Schmelze wurde 30 min bei 700°C gehalten und wie unter 1.1) weiterverarbeitet.340.8 g of ZnCl₂ were mixed with 745.5 g of KCl and melted in a graphite crucible at 700 ° C. The melt was kept at 700 ° C. for 30 min and processed as in 1.1).

2.2) Modifizierung des Komplexsalzes:2.2) Modification of the complex salt:

Dem Ansatz 2.1) wurden vor dem Aufschmelzen jeweils 10 Masse-% Modifizierungsmittel, bezogen auf den Ansatz 2.1), zugesetzt und der Ansatz wie unter 2.1) angegeben verarbeitet.Before the melting, 10% by mass of modifier, based on batch 2.1), was added to batch 2.1) and the batch was processed as indicated under 2.1).

Die erhaltenen Ergebnisse sind in der folgenden Tabelle zusammengefäßt:

Figure imgb0006
The results obtained are summarized in the following table:
Figure imgb0006

Beispiel 3:Example 3: 3.1) Herstellung des Komplexsalzes3.1) Preparation of the complex salt

298,2 g KCl und 134,5 g CuCl₂ wurden im Graphittiegel bei 500°C geschmolzen. Die Schmelze wurde 30 min bei 500°C gehalten und wie unter 1.1) weiterverarbeitet.

Figure imgb0007
298.2 g KCl and 134.5 g CuCl₂ were melted in the graphite crucible at 500 ° C. The melt was kept at 500 ° C. for 30 minutes and processed as in 1.1).
Figure imgb0007

3.2) Modifizierung des Komplexsalzes mit Na₂SO₄3.2) Modification of the complex salt with Na₂SO₄

Dem Ansatz 3.1) wurden vor dem Aufschmelzen 10 bzw. 30% Na₂SO₄ zugesetzt und der Ansatz wie unter 2.1) weiterverarbeitet.

Figure imgb0008
The approach 3.1) 10 or 30% Na₂SO₄ were added before melting and the approach as under 2.1) processed.
Figure imgb0008

3.3) Modifizierung des Komplexsalzes mit K₂SO₄3.3) Modification of the complex salt with K₂SO₄

Dem Ansatz 3.1) wurden vor dem Aufschmelzen 10 bzw. 30% K₂SO₄ zugesetzt und der Ansatz wie unter 2.1) weiterverarbeitet.

Figure imgb0009
The approach 3.1) 10 or 30% K₂SO₄ were added before melting and the approach as under 2.1) processed.
Figure imgb0009

In den Beispielen wurde die Wasseraufnahme jeweils wie folgt bestimmt: Die Proben wurden gesiebt und je 2 g der Fraktion < 125 µ auf einer Kristallisierschale gleichmäßig ausgebreitet. Die Schalen wurden in einem Gefäß mit 65% rel. Luftfeuchte gelagert und nach 100 Stunden die jeweilige Gewichtszunahme festgestellt.In the examples, the water uptake was determined as follows: The samples were sieved and 2 g of the fraction <125 μ each were spread uniformly on a crystallizing dish. The dishes were placed in a 65% rel. Stored in humidity and determined the respective weight gain after 100 hours.

Man erkennt, daß mittels der erfindungsgemäßen Modifikation die Wasseraufnahme der eingesetzten halogenhaltigen, schleifaktiven Zusatzstoffe wesentlich herabsetzbar ist.It can be seen that the water absorption of the halogen-containing, grinding-active additives used can be substantially reduced by means of the modification according to the invention.

Claims (20)

1. A halogen-containing filler for abrasive bodies on the basis of at least one metal halide or metal complex salt of the formula
Figure imgb0016
 wherein
A   is an alkali metal or ammonium,
x   is a number from 0 to 10,
MeII   is Mn, Ca, Mg, Zn, Sn, Cu, Co or Ni,
y   is a number from 0 to 2,
MeIII   is Al, B or Ti,
z   is a number from 0 to 2,
Hal   is a halogen,
E   is a number from 1 to 10,
n   is a number from 0 to 10,
B   is an alkali metal or ammonium,
f   is a number from 0 to 1,
C   is Ca, Mg, Zn, Sn or Mn,
g   is a number from 0 to 1,
e   is a number from 1 to 2,
m   is a number from 0 to 10 and
o   is a number from 0 to 10,

and/or at least one alkali chloroferrate (II, III) of the formula
Figure imgb0017
 wherein
A is an alkali metal or ammonium,
x is a number from 1 to 10,
y is a number from 0 to 1,
z is a number from 0 to 1
with the proviso that y and z
cannot be zero at the same time, the ferrate preferably being formed in combination with a basic inorganic compound, for instance zinc oxide, potassium carbonate or sodium sulfide and/or at least one mixture of a basic aluminium chloride with NaCl and/or KCl, characterized in that it contains as additive compounds either a) at least one fluorine compound or b) at least one salt of an oxygen acid selected from the group of elements consisting of nitrogen, phosphorus and sulfur, or c) at least one fluorine compound in combination with at least one of the oxygen acid salts enumerated under b).
2. A filler according to claim 1, wherein the cations of the fluorine compounds and oxygen acid salts are selected from at least one member of the group consisting of ammonium, alkali metals, alkaline earth metals, Al, B, Co, Cu, Fe, Mn, Ni, Sn, Ti and Zn.
3. A filler according to claim 1 or 2, wherein the at least one fluorine compound is selected from the group consisting of fluorides, fluorosulfates, fluorophosphates, fluoroaluminates and fluoroborates.
4. A filler according to claim 3, wherein the at least one fluorine compound is selected from the group consisting of fluorides.
5. A filler according to any one of the claims 1 to 4, wherein the additive compounds a) fluorine compound or b) oxygen acid salt or c) a combination of fluorine compound and oxygen acid salt comprise to 1 to 40 percent by weight of the halogen-containing filler.
6. A filler according to claim 5, wherein the additive compounds a) fluorine compound or b) oxygen acid salt or c) a combination of fluorine compound and oxygen acid salt comprise 3 to 20 percent by weight of the halogen-containing filler.
7. An abrasive body, in particular for metals, containing an abrasive, a binder and an active halogen-cotaining filler on the basis of at least one metal halide or metal complex salt of the formula
Figure imgb0018
 wherein
A   is an alkali metal or ammonium,
x   is a number from 0 to 10,
MeII   is Mn, Ca, Mg, Zn, Sn, Cu, Co or Ni,
y   is a number from 0 to 2,
MeIII   is Al, B or Ti,
z   is a number from 0 to 2,
Hal   is a halogen,
E   is a number from 1 to 10,
n   is a number from 0 to 10,
B   is an alkali metal or ammonium,
f   is a number from 0 to 1,
C   is Ca, Mg, Zn, Sn or Mn,
g   is a number from 0 to 1,
e   is a number from 1 to 2,
m   is a number from 0 to 10 and
o   is a number from 0 to 10,

and/or at least one alkali chloroferrate (II, III) of the formula
Figure imgb0019
 wherein
A is an alkali metal or ammonium,
x is a number from 1 to 10,
y is a number from 0 to 1,
z is a number from 0 to 1, with the
proviso that y and z cannot be zero at the same time, the ferrate preferably being formed in combination with a basic inorganic compound, for instance zinc oxide, potassium carbonate or sodium sulfide, and/or at least one mixture of a basic aluminium chloride with NaCl and/or KCl, optionally in addition to other fillers, characterized in that the halogen-containing filler comprises as additive compounds either a) at least one fluorine compound, or b) at least one salt of an oxygen acid of the group of elements consisting of nitrogen, phosphorus and sulfur, or c) at least one fluorine compound in combination with at least one oxygen acid salt enumerated under b).
8. An abrasive body according to claim 7, wherein the cations of the fluorine compounds and oxygen acid salts in the halogen-containing filler are selected from at least one member of the group consisting of ammonium, alkali metals, alkaline earth metals, Al, B, Co, Cu, Fe, Mn, Ni, Sn, Ti and Zn.
9. An abrasive body according to claim 7 or 8, wherein the at least one fluorine compound in the halogen-containing filler is selected from the group consisting of fluorides, fluorosulfates, fluorophosphates, fluoroaluminates and fluoroborates.
10. An abrasive body according to claim 9, wherein the at least one fluorine compound in the halogen-containing filler is selected from the group consisting of fluorides.
11. An abrasive body according to any one of the claims 7 to 10, wherein in the halogen-containing filler, the additive compounds a) fluorine compound or b) oxygen acid salt or c) a combination of fluorine compound and oxygen acid salt comprise 1 to 40 percent by weight of the halogen-containing filler.
12. An abrasive body according to claim 11, wherein in the halogen-containing filler, the additive compounds a) fluorine compound or b) oxygen acid salt or c) a combination of fluorine compound and oxygen acid salt comprise 3 to 20 percent by weight of the halogen-containing filler.
13. An abrasive body according to any one of the claims 7 to 12, wherein at least 5 percent by weight of the total filler are formed of the halogen-containing filler.
14. A process of producing an active halogen-containing filler for abrasive bodies, characterized in that to a halogen-containing filler on the basis of 1) at least one metal halide or metal complex salt of the formula
Figure imgb0020
 wherein
A   is an alkali metal or ammonium,
x   is a number from 0 to 10,
MeII   s Mn, Ca, Mg, Zn, Sn, Cu, Co or Ni,
y   is a number from 0 to 2,
MeIII   is Al, B or Ti,
z   is a number from 0 to 2,
Hal   is halogen,
E   is a number from 1 to 10,
n   is a number from 0 to 10,
B   is an alkali metal or ammonium,
f   is a number from 0 to 1,
C   is Ca, Mg, Zn, Sn or Mn,
g   is a number from 0 to 1,
e   is a number from 1 to 2,
m   is a number from 0 to 10 and
o   is a number from 0 to 10,

or 2) at least one alkali chloroferrate (II, III) of the formula
Figure imgb0021
 wherein
A is an alkali metal or ammonium,
x is a number from 1 to 10,
y is a number from 0 to 1,
z is a number from 0 to 1,
with the proviso that y and z
cannot be zero at the same time,
or 3) at least one mixture of a basic aluminium chloride with NaCl, KCl or NaCl + KCl, or 4) a mixture of at least two of the components of 1) to 3), or to the starting batch for its formation, additionally either a) at least one fluorine compound or b) at least one salt of an oxygen acid of the group of elements comprising nitrogen, phosphorus and sulfur, or c) at least one fluorine compound in combination with at least one of the oxygen acid salts enumerated under b).
15. A process according to claim 14, wherein a ferrate formed in combination with a basic inorganic compound, for instance zinc oxide, potassium carbonate or sodium sulfide, is employed.
16. A Process according to claim 14 or 15, wherein the cations of the fluorine compounds and oxygen acid salts are selected from at least one member of the group consisting of ammonium, alkali metals, alkaline earth metals, Al, B, Co, Cu, Fe, Mn, Ni, Sn, Ti and Zn.
17. A process according to any one of the claims 14 to 16, wherein the additive compound is at least one fluorine compound selected from the group consisting of fluorides, fluorosulfates, fluorophosphates, fluoroaluminates and fluoroborates.
18. A process according to claim 17, wherein the additive compound is at least one fluorine compound selected from the group consisting of fluorides.
19. A process according to any one of the claims 14 to 18, wherein the additive compounds a) fluorine compound or b) oxygen acid salt or c) a combination of fluorine compound and oxygen acid salt comprise 1 to 40 percent by weight of the halogen-containing filler.
20. A process according to claim 19, wherein the additive compounds a) fluorine compound or b) oxygen acid salt or c) a combination of fluorine compound and oxygen acid salt comprise 3 to 20 percent by weight of the halogen-containing filler.
EP88890179A 1987-07-17 1988-07-07 Halogen-containing fillers for abrasive articles, method for the production of these fillers and abrasive articles containing them Expired - Lifetime EP0299950B1 (en)

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AT0181087A AT394961B (en) 1987-07-17 1987-07-17 HALOGENIC FILLERS FOR ABRASIVE BODIES, METHOD FOR PRODUCING THESE FILLERS AND THE ABRASIVE BODIES CONTAINING THEM
AT1810/87 1987-07-17

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US5232468A (en) * 1990-02-13 1993-08-03 Minnesota Mining And Manufacturing Company Abrasive products bonded with color stabilized base catalyzed phenolic resin
US5110321A (en) * 1990-02-13 1992-05-05 Minnesota Mining And Manufacturing Company Abrasives containing ammonium fluoride-based grinding aid
US5219463A (en) * 1990-02-13 1993-06-15 Minnesota Mining And Manufacturing Company Abrasives containing ammonium fluoride-based grinding aid
US5110320A (en) * 1990-02-13 1992-05-05 Minnesota Mining And Manufacturing Company Abrasive products bonded with color stabilized base catalyzed phenolic resin
JPH08501340A (en) * 1992-09-15 1996-02-13 ミネソタ・マイニング・アンド・マニュファクチュアリング・カンパニー Coatable urea-aldehyde composition containing a cocatalyst, coated abrasive produced using the composition, and method for producing coated abrasive
US5523152A (en) * 1993-10-27 1996-06-04 Minnesota Mining And Manufacturing Company Organic compounds suitable as reactive diluents, and binder precursor compositions including same
US5562745A (en) * 1994-03-16 1996-10-08 Minnesota Mining And Manufacturing Company Abrasive articles, methods of making abrasive articles, and methods of using abrasive articles
DE69530976D1 (en) * 1994-03-16 2003-07-10 Minnesota Mining & Mfg ABRASIVE OBJECTS AND METHOD FOR THEIR PRODUCTION
US5702811A (en) * 1995-10-20 1997-12-30 Ho; Kwok-Lun High performance abrasive articles containing abrasive grains and nonabrasive composite grains
DE69628947D1 (en) * 1995-10-20 2003-08-07 Minnesota Mining & Mfg ABRASIVE ARTICLES CONTAINING INORGANIC PHOSPHATES
IN186662B (en) * 1997-09-08 2001-10-20 Grindwell Norton Ltd
AU2010339524B2 (en) * 2009-12-31 2013-11-28 Saint-Gobain Abrasifs Packaged abrasive articles and methods for making same
US9486896B2 (en) 2012-06-28 2016-11-08 Saint-Gobain Abrasives, Inc. Abrasive article and coating
WO2016109734A1 (en) 2014-12-30 2016-07-07 Saint-Gobain Abrasives, Inc. Abrasive tools and methods for forming same
CN108472788A (en) 2015-12-30 2018-08-31 圣戈班磨料磨具有限公司 Milling tool and its forming method

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US2216135A (en) * 1937-05-21 1940-10-01 Us Rubber Co Manufacture of abrasive articles
DE1577577A1 (en) * 1965-04-01 1970-01-02 English Abrasives Corp Ltd Abrasive or emery material
AT333142B (en) * 1972-08-07 1976-11-10 Swarovski Tyrolit Schleif ABRASIVE BODIES
AT336430B (en) * 1972-09-25 1977-05-10 Swarovski Tyrolit Schleif ABRASIVES
DE2657881A1 (en) * 1976-12-21 1978-06-22 Sia Schweizer Schmirgel & Schl ABRASIVES
DE2835543A1 (en) * 1978-08-14 1980-02-28 Riedel De Haen Ag NON-TOXIC ACTIVE FILLER IN GRINDING WHEELS
AT370024B (en) * 1980-04-01 1983-02-25 Swarovski Tyrolit Schleif GRINDING BODY WITH ABRASIVE GRAIN
CA1188103A (en) * 1981-03-20 1985-06-04 Richard H. Sioui Cbn grinding wheel
AT372894B (en) * 1981-07-20 1983-11-25 Swarovski Tyrolit Schleif GRINDING BODY
DE3441596A1 (en) * 1984-11-14 1986-05-15 Riedel-De Haen Ag, 3016 Seelze ACTIVE FILLER FOR GRINDING WHEELS

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ATE68389T1 (en) 1991-11-15

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