CN103906723A

CN103906723A - Sintered zircon particle

Info

Publication number: CN103906723A
Application number: CN201280045448.4A
Authority: CN
Inventors: 伊曼纽尔·诺妮特; 伊夫·布散特-卢
Original assignee: Saint Gobain Centre de Recherche et dEtudes Europeen SAS
Current assignee: Saint Gobain Centre de Recherche et dEtudes Europeen SAS
Priority date: 2011-07-20
Filing date: 2012-07-13
Publication date: 2014-07-02
Anticipated expiration: 2032-07-13
Also published as: WO2013011436A1; CN103906723B

Abstract

The invention relates to a sintered particle having the following chemical composition, in weight percentages on the basis of the oxides and for a total of 100%: 22% <= ZrO2 + HfO2 <= 55%, wherein HfO2 <= 2%; 14% <= SiO2 <= 35%; 6% <= Al2O3 <= 60%; 0.5% <= MgO <= 6%; B2O3 <= 5%; less than 9.0% of other oxides, and the following crystallised phases, in weight percentages on the basis of the total crystallised phases and for a total of 100%: 32% <= zircon <= 80%; 3% <= mullite <= 15%; optionally stabilised zirconia + hafnia: <= 9%; 4% <= corundum <= 57%; less than 10% of other crystallised phases; and a total porosity of no higher than 6%.

Description

The zircon particle of sintering

Technical field

The present invention relates to the zircon particle of the zircon particle of novel sintering, especially bead form, relate to the method for manufacturing these beads, and relate to these particles as abrasive material, dispersion agent in humid medium or for surface-treated purposes.

Background technology

Mining industry adopts particle for the material that adopts alternatively traditional method to be dried pre-grinding is carried out to fine grinding, is particularly useful for the fine grinding of calcium carbonate, titanium dioxide, gypsum, kaolin and iron ore.

In addition, coating industry, ink industry, dye industry, magnetic paint industry and pesticide industry use particle for disperseing and homogenizing liquid component and solids component.

Finally, Surface Processing Industry utilizes particle, for example, in particular for clean metal mould (, for the manufacture of bottle), and the chamfering of parts, rust cleaning, for the preparation of the operation of base material, shot peening or the contour peening etc. of figure layer.

Routinely, all these particles are roughly has spherical from the particle diameter of 0.005mm to 10mm, to meet above-mentioned all market.In order to use in this three classes purposes, they especially must have good wear resistance.

Especially in the field of micro-grinding, following dissimilar particle (the especially form of bead) is commercially available:

■ rounded sand grain, for example, OTTAWA sand is cheap natural product, but it is unsuitable for shredder modern pressurization, high yield.In fact, sand be low intensive, low-density, quality change is indefinite and wear equipment.

The widely used glass beads of ■, it has higher intensity, lower abrasive property and can in wider diameter range, use.

■ metal bead, especially steel ball grain, demonstrate low dark decay with respect to handled product, especially cause pollution and the coating graying of mineral filler, and its density is too high, needs special grinder.They especially cause high energy consumption, a large amount of heating of equipment and are subject to higher mechanical stress.

Also known ceramics bead.These ceramic beads have the intensity better than glass beads, higher density and excellent unreactiveness.

Ceramic beads is following type:

The ceramic beads of ■ consolidation, its conventionally by molten ceramic component, from fusing material shape globulate drop, then solidify described drop obtain, and

The ceramic beads of ■ sintering, it is conventionally by cold-forming ceramic powder, then carry out fixed obtaining by high temperature roasting.

Compared with sintered particles, consolidation particle generally includes a large amount of intergranular glassy phase of the network of filling crystal grain.Therefore the problem, being met with in their application separately by sintered particles and consolidation particle and to address these problems adopted technical scheme normally different.In addition, due to the essence difference between manufacture method, therefore, can not be used as preparing the priori of sintered particles in order to prepare composition that consolidation particle develops, vice versa.

Japanese Patent JP6106087 discloses the sintered beads based on zircon, and this sintered beads has higher than 4.46g/cm ³density.Sintered beads based on zircon also can be known from Chinese patent CN101786867 and Korean Patent KR20070096131.

In order to increase the efficiency of grinding operation, that is, for the amount of the abrasive product of specification cost, abrasive grains must be more and more wear-resisting, especially more and more wear-resisting in alkaline medium.

An object of the present invention is to meet at least in part this needs.

Summary of the invention

The present invention relates to a kind of novel sintered particles, the preferably form of bead, this particle has:

-take the weight percent based on oxide compound and total amount as 100%, described particle has following chemical constitution:

22%≤ZrO ₂+ HfO ₂≤ 55%, and HfO ₂≤ 2%;

14%≤SiO ₂≤35%；

6%≤Al ₂O ₃≤60%；

0.5%≤MgO≤6%；

B ₂O ₃≤5%；

Other oxide compounds <9.0%, and

-take the weight percent of the crystallization phases based on existing and total amount as 100%, described particle has following crystallization phases:

32%≤zircon≤80%;

3%≤mullite≤15%;

Zirconium white+hafnium oxide :≤9%, zirconium white and hafnium oxide are stabilized alternatively;

4%≤corundum≤57%;

Other crystallization phasess <10%, and

-total porosity is less than or equal to 6%.

Preferably, described sintered particles, the preferably form of bead, described particle has:

30%≤ZrO ₂+ HfO ₂≤ 55%, and HfO ₂≤ 2%;

18%≤SiO ₂≤35%；

6%≤Al ₂O ₃≤40%；

0.5%≤MgO≤6%；

B ₂O ₃≤5%；

Other oxide compounds <9.0%, and

32%≤zircon≤80%;

3%≤mullite≤15%;

4%≤corundum≤37%;

Other crystallization phasess <10%, and

-total porosity is less than or equal to 6%.

From specification sheets, will find out in more detail, contriver finds surprisingly, and the combination of these features has greatly improved wear resistance, has especially improved the wear resistance in alkaline medium.

Therefore,, according to particle of the present invention, especially bead, is specially adapted to dispersion in humid medium, micro-grinding and surface-treated application.

In addition, they demonstrate the chemical corrosivity of good media-resistant, in this medium, especially in strongly basic medium (, pH>8), carry out while grinding.For example, be therefore particularly suitable for the suspensoid of grinding calcium carbonate according to particle of the present invention.

Can also there are the one or more features in following optional feature according to sintered particles of the present invention:

-weight percent meter based on oxide compound, ZrO ₂+ HfO ₂content be greater than 25%, be preferably more than or equal 30%, be preferably more than 33%, be preferably more than 35%, be preferably more than 40% or be even greater than 42% and/or be less than 50%;

-weight percent meter based on oxide compound, SiO ₂content be greater than 16%, be preferably more than or equal 18%, be preferably more than 20%, be preferably more than 23% or be even greater than 26% and/or be less than 33% or be even less than 31%;

-weight percent meter based on oxide compound, Al ₂o ₃content be greater than 10%, be preferably more than 14%, be preferably more than 18% or be even greater than 20% and/or be less than 55%, be preferably less than 50%, be preferably less than 45%, be preferably less than or equal to 40%, be preferably less than 36%, be preferably less than 31% or be even less than 26%;

-weight percent meter based on oxide compound, the content of MgO is greater than 0.6% or be even greater than 0.7% or be even greater than 0.8% or be even greater than 0.9% or be even greater than 1.0% and/or be less than 5.0% or be even less than 4.5% or be even less than 4.0% or be even less than 3.5% or be even less than 3.0% or be even less than 2.5% or be even less than 2.0%;

-weight percent meter based on oxide compound, B ₂o ₃content be less than 0.2%, preferably approximate zero; In another embodiment, B ₂o ₃content be greater than 1.0% and be less than 3.0%;

-in one embodiment, based on the weight percent meter of oxide compound, " other oxide compounds " comprises the Y that is selected from that is greater than 0.1% ₂o ₃, oxide compound in lanthanide oxide and its mixture, be preferably selected from Y ₂o ₃and La ₂o ₃oxide compound, be preferably Y ₂o ₃oxide compound; Preferably, Y ₂o ₃and/or lanthanide oxide, preferred Y ₂o ₃and/or La ₂o ₃, preferred Y ₂o ₃content be greater than 0.7%, be preferably greater than 0.9%, and/or be less than 3.0% or be even less than 2.5%;

-in one embodiment, based on the weight percent meter of oxide compound, " other oxide compounds " comprises the CaO that is greater than 0.1%, especially when based on comprise the step d) being shaped by gelation method obtain particle time.Preferably, based on the weight percent meter of oxide compound, the content of CaO is greater than 0.3%, is preferably greater than 0.4%, is preferably greater than 0.5%, and/or is less than 4.0%, is preferably less than 3.0% or be even less than 2.0% or be even less than 1.0%;

-in one embodiment, " other oxide compounds " comprises Y ₂o ₃and/or lanthanide oxide and CaO, preferably include Y ₂o ₃and CaO;

-weight percent meter based on oxide compound, except CaO, Y ₂o ₃be less than 3.0% with " other oxide compounds " outside lanthanide oxide, be preferably less than 2.0%, be preferably less than 1.5% or be even less than 1.0%;

-except CaO, Y ₂o ₃impurity with " other oxide compounds " outside lanthanide oxide;

-preferably, the content of the oxide compound in particle according to the present invention account for described particle gross weight be greater than 99.5%, be preferably greater than 99.9% and, more preferably from about 100%;

-total amount based on crystallization phases by weight percentage, zircon content (phase ZrSiO ₄) be greater than 45%, be preferably greater than 50%, be preferably greater than 60%, be preferably greater than 65%;

-total amount based on crystallization phases by weight percentage, mullite content (phase 3Al ₂o ₃-2SiO ₂) be greater than 5%, be preferably greater than 7%, be preferably greater than 8% and/or be less than 14%, be preferably less than 12%, be preferably less than 11%;

-during sintering, generate at least a portion or even whole mullites, that is, original position is synthesized mullite;

-total amount based on crystallization phases by weight percentage, stabilized zirconium white (phase ZrO alternatively ₂)+hafnium oxide (phase HfO ₂) content be less than 5% or be even less than 4% or be even less than 3% or be even less than 2%;

-weight based on zirconium white+hafnium oxide is greater than 90% by weight percentage, be preferably more than zirconium white+hafnium oxide of 95% is monocline crystalline phase;

-total amount based on crystallization phases by weight percentage, corundum content (phase Al ₂o ₃) be greater than 8%, be preferably greater than 12%, be preferably greater than 15% and/or be less than 50%, be preferably less than 45%, be preferably less than 40%, be preferably less than or equal to 37%, be preferably less than 35%, be preferably less than 30%, be preferably less than 25% or be even less than 20%;

By weight percentage, the content of " other crystallization phasess " is less than 8% to-gross weight based on crystallization phases, be preferably less than 6% or be even less than 5% or be even less than 4% or be even less than 3% or be even less than 2%;

-preferably, " other crystallization phasess " is spinel MgAl ₂o ₄and/or trichroite and/or lime feldspar and/or quartz and/or cristobalite and/or tridymite;

-with respect to the weight of described particle by weight percentage, the content of noncrystalline phase (, glassy phase) is less than 20%, be less than 15% or be even less than 14% or be even less than 12% and/or be greater than 5% or be even greater than 7%;

-the amorphous phase that represents with oxide form comprises MgO and SiO ₂, and/or B ₂o ₃and/or Y ₂o ₃and/or lanthanide oxide and/or Al ₂o ₃and/or CaO and/or Na ₂o and/or K ₂o and/or P ₂o ₅;

-the amorphous phase that represents with oxide form comprises MgO and SiO ₂and Y ₂o ₃and Al ₂o ₃and Na ₂o and K ₂o and P ₂o ₅;

-total porosity is less than 5.5%, be preferably less than 5%, be preferably less than 4.5% or be even less than 4% or be even less than 3% or be even less than 2%;

The particle diameter that-sintered particles has is less than 10mm and/or is greater than 0.005mm;

-sintered particles is bead;

The sphericity that-sintered particles has is greater than 0.7, be preferably greater than 0.8, be preferably greater than 0.85 or be even greater than 0.9;

The density of-sintered particles is greater than 3.6g/cm ³, or be even greater than 3.7g/cm ³, or be even greater than 3.80g/cm ³, or be even greater than 3.85g/cm ³, or be even greater than 3.93g/cm ³, or be even greater than 4.00g/cm ³, or be even greater than 4.05g/cm ³, or be even greater than 4.10g/cm ³and/or be less than 4.40g/cm ³, or be even less than 4.30g/cm ³, or be even less than 4.20g/cm ³.

According to sintered particles of the present invention, preferably bead, this bead have precedence over every other material, have:

42%≤ZrO ₂+ HfO ₂≤ 50%, and HfO ₂≤ 2%;

23%≤SiO ₂≤31%；

20%≤Al ₂O ₃≤26%；

0.6%≤MgO≤2%；

B ₂O ₃≤3%；

0.9%≤Y ₂O ₃≤2.5%；

0.4%≤CaO≤1%；

Be less than 3% except ZrO ₂, HfO ₂, SiO ₂, Al ₂o ₃, MgO, B ₂o ₃, Y ₂o ₃with the oxide compound outside CaO, and

65%≤zircon≤80%;

8%≤mullite≤11%;

Zirconium white+hafnium oxide :≤3%, zirconium white and hafnium oxide are stabilized alternatively;

15%≤corundum≤20%;

Be less than other crystallization phasess of 2%, and

-weight based on particle, is less than 14% amorphous phase, and

-total porosity is less than or equal to 6%.

The invention still further relates to a kind of powder of particle, comprise be greater than by weight percentage 90%, be preferably greater than 95%, preferably approximately 100% according to particle of the present invention.

The invention still further relates to and manufacture according to the method for sintered particles of the present invention, the especially bead of sintering, the method comprises following continuous step:

A) if desired, grind one or more raw-material powder, preferably grind by common grinding, make their mixing in step c) produce the particulate mixtures with the median particle diameter that is less than 0.6 μ m,

B) alternatively, dry described particulate mixtures,

C) prepare starting material from described particulate mixtures, dry alternatively, the composition of described starting material is adjusted to obtain sintered particles when the end of step g), its composition has the composition meeting according to sintered particles of the present invention, and described starting material has and contains magnesian glass particle and/or the particle that contains magnesian glass-ceramic and/or comprise MgO and SiO ₂the particle of compound,

D) form the starting material with rough particle form,

E) alternatively, washing,

F) alternatively, dry,

G) be greater than 1330 ℃ and be less than under the sintering temperature between 1410 ℃ sintering to obtain sintered particles.

The present invention finally relates to especially and (to be particularly useful for prevent carrier extract the deep layer geology crack closure that in the well of well produce according to the powder of particle of the present invention (especially bead) as abrasive material, the dispersion agent in humid medium, carrier by the method according to this invention manufacturing, be particularly useful for oil) or heat exchange agent (for example,, for fluidized-bed) or surface-treated purposes.

definition

-" particle " refers to the single solid phase prod in powder.

-" sintering " is rough particle (granular aggregate) by heat treated the solidifying at higher than 1100 ℃, wherein, and partly or entirely consolidation of some compositions of rough particle (but not every composition) alternatively.

-" bead " refers to the particle that sphericity is greater than 0.6, and no matter how this sphericity realizes, wherein, sphericity is the minimum diameter of particle and the ratio of its maximum diameter.Preferably, bead according to the present invention has the sphericity that is greater than 0.7.

" size " of-bead (or particle) is the mean value of its overall dimension dM and its minimum size dm: (dM+dm)/2.

-conventionally use D ₅₀" median particle diameter of powder " that represent is such particle diameter: by first group and second group of the weight such as the particle of this powder is divided into, described first group and second group only comprises respectively the particle with the particle diameter that is greater than or less than median particle diameter.For example, use laser particle size meter can assess median particle diameter.

-" bead of sintering ", or more wide in range " sintered particles " refers to the solid bead (or particle) obtaining by the rough particle of sintering.

-" impurity " should be understood to the unavoidable component that finger must be introduced by raw material.Particularly, in one embodiment, belonging to the compounds being formed by the metallics of oxide compound, nitride, oxynitride, carbide, oxycarbide, carbonitride, sodium and other basic metal, iron, vanadium and chromium is impurity.As example, the impurity that can mention is Fe ₂o ₃, TiO ₂or Na ₂o.Residual carbon is according to a part for the impurity in the composition of particle of the present invention.

-when mentioning ZrO ₂or (ZrO ₂+ HfO ₂) time, should be understood to ZrO ₂hfO with trace ₂.In fact, based on ZrO ₂+ HfO ₂weight percent meter, cannot be from ZrO ₂middle chemical separation and there is a small amount of HfO of similar performance ₂always be present in natively in zirconium white source to be usually less than 3% content.Hafnia is not considered to impurity.

" precursor " of-oxide compound refers to the component that described oxide compound can be provided during according to the manufacture of particle of the present invention.

-" group of the lanthanides " is that ordination number is at 57(lanthanum) and 71(lutetium) between chemical element, lanthanum and lutetium are included in described group of the lanthanides.

For the sake of clarity, term " ZrO ₂", " HfO ₂" and " Al ₂o ₃" being used to refer to the content of these oxide compounds in composition, " zirconium dioxide ", " hafnium oxide " and " corundum " are used to refer to respectively by ZrO ₂, HfO ₂and Al ₂o ₃the crystallization phases of these oxide compounds that form.But these oxide compounds also can be used as other and exist mutually, especially with zircon (ZrSiO ₄) form or mullite (3Al ₂o ₃-2SiO ₂) form.

Unless otherwise indicated, all per-cents otherwise in this specification sheets are the weight percents based on oxide compound.

Unless otherwise indicated, otherwise " comprising one ", " comprising one " or " thering is one " refer to and comprise " at least one ".

specifically describe

In order to manufacture according to sintered particles of the present invention, can follow the above-described and technique to step g) by the step a) presenting in detail below.

In step a), raw-material powder can be ground individually, or preferably altogether grinds, if they are mixed with the ratio that is suitable for preparing initial charge, in step c), can not produce the particulate mixtures with the median particle diameter that is less than 0.6 μ m.This grinding can be wet-milling.

Preferably, grind or grind to be altogether performed and make the median particle diameter of described particulate mixtures be less than 0.5 μ m, preferably be less than 0.4 μ m.

Preferably, powder used, especially zircon ZrSiO ₄powder, aluminium oxide Al ₂o ₃powder, Y ₂o ₃powder, lanthanide oxide powder, contain magnesian glass powder, contain magnesian glass ceramic powder, comprise MgO and SiO ₂the powder of compound and the powder of mullite, its median particle diameter having is less than respectively 5 μ m or is even less than 3 μ m, is less than 1 μ m, is less than 0.7 μ m, is preferably less than 0.6 μ m, is preferably less than 0.5 μ m or is even less than 0.4 μ m.Advantageously, the median particle diameter having when every kind of powder in these powder is less than 0.6 μ m, when being preferably less than 0.5 μ m or being even less than 0.4 μ m, and step a) is optional.

Preferably, the specific surface area that zircon powder used calculates by BET method (specific surface area method) is greater than 5m ²/ g, be preferably greater than 8m ²/ g, be preferably greater than 10m ²/ g and/or be less than 30m ²/ g.Advantageously, facilitate conventionally with the grinding in the step a) of form of suspension by this point.In addition, can be reduced in the sintering temperature in step f).

Preferably, the median particle diameter that alumina powder used has is less than 7 μ m, is preferably less than 6 μ m or is even less than 3 μ m or is even less than 2 μ m or is even less than 1 μ m or is even less than 0.5 μ m.Advantageously, facilitate alumina powder and silicon-dioxide from existing particulate mixtures or produce during step g) to form mullite by this point.

In step b), alternatively, if obtain raw-material abrasive flour by wet lapping, for example in baking oven or by spraying, be dried raw-material abrasive flour.Preferably, the time length of adjusting temperature and/or drying step makes the content of residual water of raw-material powder be less than 2% or be even less than 1.5%.

In step c), at room temperature prepare initial charge, this initial charge comprises zircon ZrSiO ₄powder, Al ₂o ₃powder and optional Y ₂o ₃and/or lanthanide oxide and/or contain magnesian glass and/or contain magnesian glass-ceramic and/or comprise MgO and SiO ₂compound and/or the powder of mullite.

These powder also can adopt the powder of the precursor of these oxide compounds of equivalent introducing to replace at least in part.

Particularly, these crystallization phasess that a part or even whole particles according to zircon of the present invention and/or mullite can come to exist in comfortable initial charge.

The powder that contains magnesian glass powder and/or contain magnesian glass-ceramic preferably contains and is greater than 40%, is preferably more than 50% or be even greater than 60% or be even greater than 70% or be even greater than the silicon-dioxide of 80 % by weight.They also can not contain silicon-dioxide.

Comprise MgO and SiO ₂compound, also preferably include Al ₂o ₃.Preferably, described compound is selected from talcum, trichroite and its mixture.Preferably, described compound is trichroite.Particularly, based on the weight of initial charge, the amount of the trichroite that initial charge can contain is preferably greater than 3.8%, be preferably greater than 4%, be preferably greater than 5% and/or be less than 30%, be preferably less than 25%, be preferably less than 20% or be even less than 15 % by weight.

Provide the powder of oxide compound or precursor preferably selected, make based on oxide compound by weight percentage, " other oxide compounds " is (except ZrO ₂, HfO ₂, SiO ₂, Al ₂o ₃, MgO and B ₂o ₃outside oxide compound) total content be less than 3%.

Based on the weight of initial charge, zircon powder (, the ZrSiO that initial charge contains ₄particle) amount be greater than by weight 32%, be preferably greater than 45%, be preferably greater than 50%, be preferably greater than 60%, be preferably greater than 65% and/or be less than 80%.

Based on the weight of initial charge, alumina powder (, the Al that initial charge contains ₂o ₃particle) amount be greater than 4%, be preferably greater than 8%, be preferably greater than 12%, be preferably greater than 15% and/or be less than 55%, be preferably less than 50%, be preferably less than 45%, be preferably less than 40%, be preferably less than 35%, be preferably less than 30%, be preferably less than 25 % by weight.Preferably, described alumina powder is active oxidation aluminium powder form and/or calcined oxide aluminium powder form and/or transition state of alumina powder.Preferably described alumina powder is active oxidation aluminium powder form.

In one embodiment, based on crystallization phases by weight percentage, initial charge comprises and is less than 9%, is less than 5%, is less than 2% zirconium dioxide (, ZrO ₂particle) or even do not comprise zirconium dioxide.In fact, zirconium dioxide or the even whole zirconium whites of a part can originate from the decomposition of zircon during sintering in step g).

In one embodiment, based on crystallization phases by weight percentage, initial charge comprises and is less than 15%, is less than 10%, is less than 5% mullite, or even do not comprise mullite.In step g), during sintering, preferably can generate in situ a part of mullite or even whole mullites from the precursor that is selected from following material:

-contain magnesian glass, preferably include SiO ₂, and/or

-contain magnesian glass-ceramic, and/or

-comprise MgO and SiO ₂compound, described compound preferably also comprises Al ₂o ₃(preferably described compound is selected from talcum and trichroite, preferably described compound is trichroite), and/or

-derive from zircon ZrSiO ₄resolve into zirconium white ZrO ₂with silicon-dioxide SiO ₂aluminum oxide and silicon-dioxide.

By the precursor of mullite mentioned above and/or by comprising that magnesian other compounds can provide MgO.

In one embodiment, initial charge comprises Y ₂o ₃and/or the powder of the particle of lanthanide oxide, Y preferably ₂o ₃powder and the La of particle ₂o ₃the powder of particle, preferably Y ₂o ₃the powder of particle, based on the weight of initial charge, the amount of the powder of the particle comprising is greater than 0.1%, be preferably more than 0.7%, be preferably more than 0.9% and/or be preferably less than 3% or be even less than 2.5 % by weight.

In one embodiment, three embodiments that combination has above just been described.

In one embodiment, based on the weight of initial charge, initial charge comprises pulverous silicon-dioxide (, SiO ₂particle), its content is preferably greater than 0.5%, be preferably greater than 1%, be preferably greater than 2% and/or be less than 10%, be preferably less than 8%, be preferably less than 5 % by weight.

Preferably, in initial charge, deliberately do not introduce except ZrO is provided ₂+ HfO ₂, SiO ₂, Al ₂o ₃, MgO and Y alternatively ₂o ₃and/or lanthanide oxide and/or B ₂o ₃and/or starting material outside the starting material of the precursor of CaO and they, other oxide compounds of existence are impurity.

In addition, initial charge can comprise solvent (preferably water), and the amount of solvent is suitable for the method for the shaping in step d).

Those skilled in the art knows, and initial charge is suitable for the method for the shaping in step d).

Be shaped and especially can come from the method for gelation.For this object, solvent (preferably water) is added to initial charge with prepare suspension.

The weight percent content of the dry-matter that preferably, suspension has is between 50% to 70%.

Suspension can also comprise one or more of following ingredients:

-dispersion agent, based on the weight percent meter of dry-matter, concentration from 0 to 10%;

-surface tension modifier, based on the weight percent meter of dry-matter, concentration from 0 to 3%;

-jelling agent or " gelifying agent ", based on the weight percent meter of dry-matter, concentration from 0 to 2%.

Those skilled in the art knows dispersion agent, surface tension modifier and jelling agent.

With regard to embodiment, can mention:

-with regard to dispersion agent, sodium polymethacrylate or ammonium polymethacrylate class, sodium polyacrylate or ammonium polyacrylate class, polyacrylic acid (sodium or ammonium salt) or other polyelectrolyte classes, citric acid salt (for example ammonium citrate), sodium phosphate class and carbonates;

-surface tension modifier, for example, the organic solvent of fatty alcohol;

-jelling agent, for example, natural polysaccharide.

During manufacturing step subsequently, all these compositions disappear, but they still can keep trace.

Preferably, the powder of oxide compound and/or precursor is added to water in ball mill and the mixture of dispersion agent/deflocculation agent.After stirring, add water, wherein, jelling agent is dissolved to obtain suspension in advance.

If being shaped is the result of extruding, can add thermoplastic polymer and thermosetting polymer to initial charge.

In step d), can adopt for the manufacture of sintered particles, any ordinary method of the shaping of sintered beads especially.

In these methods, can mention:

-prilling process, for example, adopts tablets press, fluidized bed pelletizer or granulation disc;

-gel method,

-injection moulding or the method for extruding, and

-process for stamping.

In gel method, obtain the drop of above-described suspension through calibration hole by suspension flow.The drop that leaves hole falls into the bath of gelating soln (be suitable for react with jelling agent ionogen), wherein, drop roughly become spherical after, drop hardening.

In step e), alternatively, the rough particle that washing obtains in previous step, for example, washes with water.

In step f), alternatively, for example, the dry rough particle being washed alternatively in baking oven.

In step g), the rough particle that is washed alternatively and/or is dried is sintered.Preferably, preferably under atmospheric pressure, preferably in electric arc furnace, in air, carry out sintering.

Being greater than 1330 ℃, be preferably greater than 1340 ℃, be preferably greater than 1350 ℃, be preferably greater than 1360 ℃, be preferably greater than 1370 ℃ and be less than 1410 ℃, be preferably less than 1400 ℃, be preferably less than the sintering in performing step g) at the temperature of 1390 ℃.The sintering temperature that equals 1375 ℃ is most suitable.The sintering temperature that is less than 1330 ℃ can not obtain the particle with the total porosity that is less than or equal to 6%, and in the time that original position generates mullite, the amount of mullite is more than or equal to 3%.On the contrary, be greater than the excessive decomposition that the sintering temperature of 1410 ℃ causes zircon, this is disadvantageous to wear resistance.

Preferably, sintering duration is between 2 hours to 5 hours.If sintering duration equals 4 hours, be most suitable.

The sintered particles obtaining preferably has the form of the bead of the minimum diameter between 0.005mm and 10mm.

Can apply following rule well-known to those having ordinary skill in the art to obtain according to sintered particles of the present invention:

-increase the amount of the zircon in sintered particles: increase the amount of zircon in initial charge and/or reduce sintering temperature so that zircon is resolved into silicon-dioxide and zirconium dioxide by restriction;

-be reduced in the amount of zircon in sintered particles: reduce the amount of zircon in initial charge and/or increase sintering temperature;

-increase the amount of the corundum in sintered particles: increase the amount of corundum in initial charge and/or reduce sintering temperature so that the original position of restriction mullite is shaped;

-be reduced in the amount of corundum in sintered particles: be reduced in the amount of corundum in initial charge and/or increase sintering temperature;

-increasing the zirconic amount in sintered particles: in increase initial charge, zirconic amount and/or reduction sintering temperature are so that zircon is resolved into silicon-dioxide and zirconium dioxide by restriction;

-increase the amount of the mullite in sintered particles: increase the amount of mullite in initial charge and/or increase sintering temperature to promote the original position of mullite to be shaped;

-reduce the amount of the mullite in sintered particles: reduce the amount of mullite in initial charge and/or reduce sintering temperature so that the original position of restriction mullite is shaped;

-reduce the total porosity with the sintered particles that limits initial charge: make sintering temperature approach the preferable range of sintering temperature and/or increase the amount of Powdered silicon-dioxide in initial charge and/or increase to comprise MgO and SiO in initial charge ₂the amount of compound.

Sintered particles according to the present invention is specially adapted to as abrasive material or the dispersion agent in humid medium and for surface treatment.Therefore, the invention still further relates to most particles, especially according to the bead of bead of the present invention or the method according to this invention manufacturing, as the purposes of abrasive material or the dispersion agent in humid medium.

But, should note, can make them be suitable for other purposes according to the performance of particle of the present invention (especially their physical strength, their density and the easy degree of their production), especially as propping agent or heat exchange agent or for surface treatment (especially by particle polishing according to the present invention).

Therefore, the invention still further relates to and be selected from levitation device, shredder, for the device of surface-treated equipment and heat exchanger, described device comprises the powder according to particle of the present invention.

Embodiment

embodiment

Following non-limiting examples provides for the purpose of illustrating the invention.

measurement scheme

Following method is for the specified property of the multiple mixture of the bead of definite sintering.They provide the excellence of the truth of moving in micro-abrasive application to simulate.

In order to determine so-called " planetary " wear resistance, 20ml(is used to scale test tube measured volume) particle diameter weigh at the bead to be tested between 1.2mm to 1.4mm that (weight is m ₀), then put it into a bowl in 4 bowls high speed planetary-type grinding machine, that be 125ml with the volume that fine and close sintered alumina applies of the PM400 type of manufacturing by RETSCH.By the silicon carbide of the 2.2g being produced by Presi, (median particle diameter D50 is that 23 μ m) join in the same bowl that holds bead with the water of 40ml.This bowl is closed and sets the speed rotation (planetary motion) with 400rev/min, and the reversion of sense of rotation per minute once continues 1.5 hours.The content of bowl subsequently on 100-μ m sieve washing with remove residual silicon carbide and grinding during the material that comes off due to wearing and tearing.After the sieve top sieve of 100-μ m divides, bead is dried at 100 ℃ to 3 hours (weight m that weigh subsequently in baking oven ₁).Described bead (weight m ₁) again put into one of them bowl of the suspension (concentration as hereinbefore and consumption) with SiC, and carry out the new circulation of the grinding identical with last circulation.The content of bowl subsequently on 100-μ m sieve washing with remove residual silicon carbide and grinding during the material coming off due to wearing and tearing.After the sieve top sieve of 100-μ m divides, bead is dried at 100 ℃ to 3 hours (weight m that weigh subsequently in baking oven ₂).Described bead (weight m ₂) again put into one of them bowl of the suspension (concentration as hereinbefore and consumption) with SiC and carry out the new circulation of the grinding identical with last circulation.The content of bowl subsequently on 100-μ m sieve washing with remove residual silicon carbide and grinding during the material that comes off due to wearing and tearing.After the sieve top sieve of 100-μ m divides, at 100 ℃, bead is dried to 3 hours in baking oven, (weight m subsequently weighs ₃).

Planetary wearing and tearing (PW) represent with per-cent (%) and equal the weight loss of bead with respect to bead initial weight, or: 100(m ₀-m ₃)/(m ₀); In table 1, provide result PW.

Can think, if fruit product with respect at least improving 15% with reference to embodiment 1 in planetary wearing and tearing (PW), result is gratifying.

For determine so-called " in alkaline medium (that is, and pH value higher than 8 medium in) " wear resistance, the charging of bead to be tested is screened between 1.8mm to 2mm on square hole sieve.The bead that is 1.04 liters by apparent volume (the weight m' that weighs ₀).Bead is placed in the horizontal mill (useful volume of 1.2L) with the Netzsch LME1 type of eccentric steel disk subsequently.Calcium carbonate CaCO ₃the pH value that has of waterborne suspension be 8.2, contain 70% dry-matter, wherein, 40% particulate has the particle diameter that is less than 1 μ m by volume, this suspension passes through shredder continuously with the flow velocity of 5 ls/h.Shredder starts gradually until to realize in the linear velocity of end of dish be 10m/s.The operated time length t of shredder equals 6 hours, then stops.Bead water rinses, and takes out carefully then washing and dry from shredder.Then they are weighed (weight m').Wear rate V(represents with Grams Per Hour) determine by following formula: V=(m' ₀-m')/t.

The charging of bead is collected and supplements (m' ₀-m') gram new bead with repeatedly (n time) of repetitive operation as required, it is relative that the milling time that makes accumulation is at least that the difference between 40 hours and the wear rate that makes to calculate in step n and step n-1 is less than 15%().Wearing and tearing (BW) in alkaline medium are measured wear rate in this stable condition (normally 42 hours).In table 1, provide BW result.

Can think, as fruit product at least improves 20% in the wear resistance (BW) of alkaline medium with respect to the wear resistance with reference to embodiment 1, result is gratifying especially.

The crystallization phases existing in sintered particles according to the present invention is measured by X-ray diffraction, for example, and by the diffractometer type instrument X'Pert PRO that is provided with copper DX pipe from Panalytical company.Use this equipment to carry out obtaining of diffraction pattern on angular range 2 θ between 5 ° to 80 °, wherein step-length is 0.017 °, and gate time is 60s/ step-length.Front lens comprises the fixing programmable divergent slit that uses 1/4 °, the Soller slit of 0.04rad, and mask equals 10mm and fixing anti-scatter slit is 1/2 °.Sample rotates to limit preferred direction around the axis of himself.Rear lens comprises the fixing programmable anti-scatter slit that uses 1/4 °, the Soller slit of 0.04rad, and Ni spectral filter.The pattern obtaining adopts the High Score Plus software with Rietveld matching to process, the section of mullite is at " Crystal structure and compressibility of3:2mullite " (Balzar etc., American Mineralogist; In December, 1993; The 78th volume; No.11-12; The 1192nd page the-the 1196th page) the middle Al describing _4.5si _1.5o _9.74section.Multiple parameters are the maximum yojan for the value of " R Bragg " by matching.

For example, by X-ray diffraction (, by the diffractometer type instrument X'Pert PRO that is provided with copper DX pipe from Panalytical company), measure according to the amount of the amorphous phase existing in sintered particles of the present invention.Carry out obtaining of diffraction pattern with this equipment, be determined in the same way the crystalline phase in particle.The weight of the sample based on zinc oxide according to the present invention and sintered particles, method used comprises: in the case of existing the amount of zinc oxide to equal 20%, add the standard holocrystalline of known quantity.

Total porosity (representing with %) adopts following formula to evaluate:

Total porosity=100 × (1 – (d _bead/ d _{the bead grinding})), wherein,

-d _beadaccording to the method for the volume of the gas (being helium in this case) based on measurement displacement, use helium specific gravity flask (from

the AccuPyc1330 of company) obtain grinding before bead density, and

-d _{the bead grinding}it is the powder density of grinding bead 40s, then screening (making the powder only sieving through 160-μ m for measuring) acquisition in the circular dry grinding machine of being manufactured by Aurec.

fabrication scheme

From the about 8m of specific surface area ²/ g and median particle diameter equal the zircon powder of 1.5 μ m; Purity equal 99.5% and median particle diameter be less than the alumina powder of 5 μ m; Purity be greater than 95% and median particle diameter be less than the cordierite powder of 63 μ m; And according to performed embodiment, median particle diameter be less than 53 μ m and the ignition loss amount carried out at 1000 ℃ between 10% to 15% and SiO ₂+ Al ₂o ₃the total content clay that is greater than 82%; Be greater than based on rare earth oxide purity 99.9% and median particle diameter be less than the Y of 10 μ m ₂o ₃powder, prepare the bead of sintering.

These powder are mixed to be ground altogether until obtain the particulate mixtures with the median particle diameter that is greater than 0.4 μ m subsequently in humid medium.This particulate mixtures of subsequent drying.

Prepare from this particulate mixtures the initial charge being formed by waterborne suspension subsequently, this waterborne suspension comprises: based on the weight percent meter of dry-matter, the dispersion agent of the dispersion agent of 0.5% carboxylic acid type, 0.6% sodium phosphate type and 0.4% jelling agent (, the polysaccharide of alginates).

Ball mill is the good homogeneity with acquisition initial charge for described preparation: the solution that first preparation contains jelling agent.Then, particulate mixtures and dispersion agent are added to the water.Then add the solution that contains jelling agent.The mixture obtaining is stirred 8 hours.By use company

the particle diameter that the Sedigraph5100 particle-size analyzer (sedigraph) of selling carrys out monitor particles by sedimentation (median particle diameter <0.4 μ m), adds appropriate water to obtain the waterborne suspension that has 66% dry-matter and have the viscosity (using LV3 axle to measure with the speed Brookfield viscometer of 20rev/min) that is less than 5000 centipoises.Thereby the pH value of suspension approximates 8.

Suspension is forced through calibration hole with certain flow velocity, and this flow velocity can make to obtain the bead of the 1.2mm to 1.4mm in the content of this embodiment after sintering.The drop of suspension falls into the coagulation bath based on ionogen (salt of divalent cation), and reacts with jelling agent.Rough bead is collected, washs, then at 80 ℃, is dried to remove moisture.Bead is transferred to sintering oven subsequently, and in this sintering oven, these beads are heated to required sintering temperature Ts with the speed of 100 ℃/h.Under temperature T s, through after the steady stage of 4 hours, can reduce temperature by naturally cooling.

result

What obtain the results are summarized in following table 1.

Is the zircon bead of sintering conventional in abrasive application with reference to bead (not being according to bead of the present invention) in embodiment " with reference to 1 ", and its composition approaches the composition of the embodiment 4 in US2004/007789.

Surprisingly, these embodiment show, with compared with bead, test bead according to the present invention demonstrates significant performance.

According to the comparison of the product of embodiment 2, embodiment 4, embodiment 13 and embodiment 14, under the temperature T s that equals 1375 ℃ and except MgO, substantially having identical chemico-analytic all sintered products shows: the impact in the wear resistance of MgO at bead: contain respectively 0.39% and 0.03% MgO according to the product of embodiment 13 and embodiment 14, with respect to according to the product with reference to 1, there is respectively poor wear resistance PW% according to the product of embodiment 13 and embodiment 14.Contain respectively 0.69% and 1.03% MgO according to the product of embodiment 2 and embodiment 4, with respect to according to the product with reference to 1, there is respectively the wear resistance PW% of improvement according to the product of embodiment 2 and embodiment 4.

The such fact of comparative descriptions according to the product of embodiment 1 and embodiment 2: exceed 6% if total porosity increases, no longer improve with respect to the Wear Resistance PW% with reference to 1.

The product of embodiment 11 and embodiment 12 shows, if mullite content equals 3%, wear resistance PW% improves respectively 17% and 36% with respect to the product with reference to 1.Demonstrate according to other embodiments of the invention, the mullite content (embodiment 4) for 10%, wear resistance PW% increases until it reaches maximum value.

With respect to from reference to 1 product, according to the product of embodiment 17 (not being according to product of the present invention) demonstration place, equal 17% mullite content and do not improve wear resistance PW%.

According to the comparison of the product of embodiment 7, embodiment 9 and embodiment 10, equaling under 1375 ℃ of temperature T s and except Y ₂o ₃outside substantially there are identical chemico-analytic all sintered products and demonstrate, Y ₂o ₃impact in the wear resistance of bead: if Y ₂o ₃content increase, wear resistance PW% increase.With respect to the product with reference to 1, according to the Y with 1.09% ₂o ₃the product of the embodiment 10 of content demonstrates, and on wear resistance PW%, improves 44%, and, with respect to the product with reference to 1, Y ₂o ₃content equal respectively 0.7% and 0.2% on wear resistance PW%, improve respectively 35% and 31% according to embodiment 7 with according to the product of embodiment 9.

With respect to reference 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5, embodiment 7 and embodiment 8 relatively demonstrate, the sintering temperature Ts that equals 1425 ℃ has reduced wear resistance PW%, but the identical product of institute's sintering has improved this abradability under the temperature T s that equals 1375 ℃.

With respect to the product with reference to 1, demonstrate on wear resistance BW% and improve 45% according to the product of embodiment 10.

In an embodiment, zirconium white and hafnium oxide are approximate 100% oblique crystals.

The product of embodiment 4 and embodiment 10 is preferred product.

Certainly, the invention is not restricted to above-described embodiment and embodiment.Particularly, other gel systems are suitable for manufacturing according to ceramic beads of the present invention.Therefore, US5466400, FR2842438 and US4063856 have described applicable sol-gel technique.FR2842438 and US4063856 are suitable for the gel systems that is similar to above-described system (based on alginate), but US5466400 has described extremely different gel systems.

It is also contemplated that the method described and by punching press or form the method for bead by granulation in US2009/0036291.

Can combine multiple embodiments.

Claims

1. a sintered particles,

22%≤ZrO ₂+ HfO ₂≤ 55%, and HfO ₂≤ 2%;

14%≤SiO ₂≤35%；

6%≤Al ₂O ₃≤60%；

0.5%≤MgO≤6%；

B ₂O ₃≤5%；

Other oxide compounds <9.0%, and

32%≤zircon≤80%;

3%≤mullite≤15%;

Zirconium white+hafnium oxide :≤9%, described zirconium white and hafnium oxide are stabilized alternatively;

4%≤corundum≤57%;

Other crystallization phasess <10%, and

-total porosity is less than or equal to 6%.

2. according to the sintered particles described in last claim,

30%≤ZrO ₂+ HfO ₂≤ 55%, and HfO ₂≤ 2%;

18%≤SiO ₂≤35%；

6%≤Al ₂O ₃≤40%；

0.5%≤MgO≤6%；

B ₂O ₃≤5%；

Other oxide compounds <9.0%, and

32%≤zircon≤80%;

3%≤mullite≤15%;

4%≤corundum≤37%;

Other crystallization phasess <10%, and

-total porosity is less than or equal to 6%.

3. according to sintered particles in any one of the preceding claims wherein, wherein: 35%≤ZrO ₂+ HfO ₂.

4. according to the sintered particles described in last claim, wherein: 40%≤ZrO ₂+ HfO ₂.

5. according to sintered particles in any one of the preceding claims wherein, wherein: SiO ₂>23% and/or Al ₂o ₃>10% and/or MgO>0.6%.

6. according to sintered particles in any one of the preceding claims wherein, wherein: SiO ₂<31% and/or Al ₂o ₃<36% and/or MgO<5.0%.

7. according to sintered particles in any one of the preceding claims wherein, wherein: 31%>Al ₂o ₃>18%.

8. according to sintered particles in any one of the preceding claims wherein, wherein: 2.0%>MgO>0.8%.

9. according to sintered particles in any one of the preceding claims wherein, wherein: 3.0>B ₂o ₃>1.0%.

10. according to the sintered particles described in any one in claim 1 to 8, wherein: B ₂o ₃<0.2%.

11. according to sintered particles in any one of the preceding claims wherein, comprises the Y that is selected from that is greater than 0.1% ₂o ₃, oxide compound in lanthanide oxide and its mixture.

12. according to the sintered particles described in last claim, wherein: be selected from Y ₂o ₃, lanthanide oxide and its mixture the content of described oxide compound between 0.7% and 3.0%.

13. according to the sintered particles described in any one in front two claims immediately, wherein: be selected from Y ₂o ₃, lanthanide oxide and its mixture described oxide compound be Y ₂o ₃and/or La ₂o ₃.

14. according to the sintered particles described in last claim, wherein: be selected from Y ₂o ₃and/or La ₂o ₃described oxide compound be Y ₂o ₃.

15. according to sintered particles in any one of the preceding claims wherein, comprises the CaO that is greater than 0.1%.

16. according to the sintered particles described in last claim, wherein: 0.3%<CaO<4.0%.

17. according to the sintered particles described in last claim, wherein: CaO<1.0%.

18. according to sintered particles in any one of the preceding claims wherein, wherein: except ZrO ₂, HfO ₂, SiO ₂, Al ₂o ₃, MgO, B ₂o ₃, CaO, Y ₂o ₃be less than 3.0% with the content of the oxide compound outside described lanthanide oxide.

19. according to the sintered particles described in last claim, wherein: except ZrO ₂, HfO ₂, SiO ₂, Al ₂o ₃, MgO, B ₂o ₃, CaO, Y ₂o ₃be less than 2.0% with the content of the oxide compound outside described lanthanide oxide.

20. according to the sintered particles described in last claim, wherein: except ZrO ₂, HfO ₂, SiO ₂, Al ₂o ₃, MgO, B ₂o ₃, CaO, Y ₂o ₃be less than 1.5% with the content of the oxide compound outside described lanthanide oxide.

21. according to sintered particles in any one of the preceding claims wherein, wherein: the content of described oxide compound account for described particle gross weight be greater than 99.5%.

22. according to sintered particles in any one of the preceding claims wherein, and the zircon content having is greater than 45%.

23. according to the sintered particles described in last claim, wherein: described zircon content is greater than 50%.

24. according to the sintered particles described in last claim, wherein: described zircon content is greater than 60%.

25. according to sintered particles in any one of the preceding claims wherein, the mullite content having is greater than 5% and/or be less than 14%.

26. according to the sintered particles described in last claim, wherein: described mullite content is greater than 7% and/or be less than 12%.

27. according to the sintered particles described in last claim, wherein: described mullite content is greater than 8% and/or be less than 11%.

28. according to sintered particles in any one of the preceding claims wherein, wherein: synthetic described mullite during sintering.

29. according to sintered particles in any one of the preceding claims wherein, and the stabilized zirconium white alternatively having and the content of hafnium oxide are less than 5%.

30. according to sintered particles in any one of the preceding claims wherein, and the corundum content having is greater than 8% and/or be less than 35%.

31. according to the sintered particles described in last claim, wherein: described corundum content is greater than 12% and/or be less than 30%.

32. according to the sintered particles described in last claim, wherein: described corundum content is greater than 15%.

33. according to sintered particles in any one of the preceding claims wherein, and the content of " other crystallization phasess " having is less than 8%.

34. according to the sintered particles described in last claim, wherein: the content of described " other crystallization phasess " is less than 5%.

35. according to the sintered particles described in last claim, wherein: the content of described " other crystallization phasess " is less than 3%.

36. according to sintered particles in any one of the preceding claims wherein, and with the weight percent meter with respect to described particle, the amount of the amorphous phase having is less than 20% and be greater than 5% by weight.

37. according to the sintered particles described in last claim, wherein: with the weight percent meter with respect to described particle, the amount of amorphous phase is less than 15% and/or be greater than 7% by weight.

38. according to the sintered particles described in last claim, wherein: with the weight percent meter with respect to described particle, the amount of amorphous phase is less than 12% by weight.

39. according to the sintered particles described in any one in first three items claim immediately, wherein: the amorphous phase representing with oxide form comprises MgO and SiO ₂, and/or B ₂o ₃and/or Y ₂o ₃and/or lanthanide oxide and/or Al ₂o ₃and/or CaO and/or Na ₂o and/or K ₂o and/or P ₂o ₅.

40. according to the sintered particles described in last claim, wherein: the amorphous phase representing with oxide form comprises MgO, SiO ₂, Na ₂o, K ₂o and P ₂o ₅.

41. according to sintered particles in any one of the preceding claims wherein, and the total porosity that described particle has is less than 5.5%.

42. according to the sintered particles described in last claim, the total porosity having is less than 5%.

43. according to the sintered particles described in last claim, the total porosity having is less than 4%.

44. according to sintered particles in any one of the preceding claims wherein, and the sphericity having is greater than 0.6, and described sphericity is the ratio of the minimum diameter of described particle and the maximum diameter of described particle.

45. according to the sintered particles described in last claim, the sphericity having is greater than 0.7.

46. according to the sintered particles described in last claim, the sphericity having is greater than 0.8.

47. according to sintered particles in any one of the preceding claims wherein, and the particle diameter having is less than 10mm and is greater than 0.005mm.

48. 1 kinds of powder, comprise be greater than by weight percentage 90% according to particle in any one of the preceding claims wherein.

49. 1 kinds of manufactures are according to the method for the sintered particles described in any one in claim 1 to 47, and described method comprises following continuous step:

A) if desired, grind one or more raw-material powder, preferably grind by common grinding, make in step c) their particulate mixtures with the median particle diameter that is less than 0.6 μ m that is mixed to get,

B) alternatively, dry described particulate mixtures,

C) prepare starting material from the described particulate mixtures being dried alternatively, the composition of described starting material is adjusted to obtain sintered particles in the time that step g) finishes, the composition of this sintered particles meets the composition according to sintered particles in any one of the preceding claims wherein, and described starting material has and contains magnesian glass particle and/or the particle that contains magnesian glass-ceramic and/or comprise MgO and SiO ₂the particle of compound,

D) starting material is configured as to the form of rough particle,

E) alternatively, washing,

F) alternatively, dry,

G) be greater than 1330 ℃ and be less than sintering under the sintering temperature between 1410 ℃.

50. according to the method described in last claim, wherein, in step c), the silicon-dioxide that the powder packets that contains magnesian glass powder and/or contain magnesian glass-ceramic is greater than 40% containing weight percent.

51. according to the method described in last claim, wherein: in step c), and the silicon-dioxide that the powder packets that contains magnesian glass powder and/or contain magnesian glass-ceramic is greater than 60% containing weight percent.

52. according to the method described in any one in first three items claim immediately, and wherein, in step c), described compound comprises MgO and SiO ₂, also comprise Al ₂o ₃.

53. according to the method described in last claim, wherein: described compound is selected from talcum, trichroite and its mixture.

54. according to the method described in last claim, wherein: described compound is trichroite.

55. 1 kinds of objects, are selected from suspension, shredder, for surface-treated equipment and heat exchanger, and described object comprises according to the powder of the particle described in claim 48.