CN102503546A - Antioxidant impregnating agent of graphite die used for hot-pressing sintering of diamond tool and preparation method and processing method thereof - Google Patents
Antioxidant impregnating agent of graphite die used for hot-pressing sintering of diamond tool and preparation method and processing method thereof Download PDFInfo
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Abstract
The invention discloses an antioxidant impregnating agent of graphite dies used for hot-pressing sintering of diamond tools and preparation method and processing method of the antioxidant impregnating agent of graphite dies. The antioxidant impregnating agent is made from compound phosphates, high temperature-resistant curing agents, compression-resistant reinforcing agents, pH regulators and water. The method comprises the following steps of: firstly adding water into compound phosphates and heating and mixing to dissolve completely to obtain a homogenous transparent liquid; then adding high temperature-resistant curing agents and compression-resistant reinforcing agents to the transparent liquid and heating and mixing until homogenous; and finally adding pH regulators to adjust the pH value of the liquid mixture to 1 to 3, to obtain the solution of antioxidant impregnating agent. The solution of antioxidant impregnating agent, prepared by the invention, is applied to antioxidant treatment of a graphite die by impregnation; and the related performances of the graphite die are tested after treatment. The graphite die treated by the antioxidant impregnating agent substantially retains electrical properties of graphite, has an electrical resistivity of not more than 20 omega mm<2>/m, and is substantially not be oxidized at a temperature below 800 DEG C. The porosity is reduced by 50% and the compression strength is greatly increased.
Description
Technical field
The present invention relates to a kind of anti-oxidant soaker, particularly relate to a kind of thermal pressing sintering diamond tool with the anti-oxidant soaker of graphite jig and compound method and treatment process.
Background technology
Thermal pressing sintering diamond tool is used graphite jig, in the diamond tool manufacturing processed, is undertaking the dual function that Heating element and mould support, and the quality good or not of graphite jig directly has influence on the dimensional precision, face shaping of diamond tool etc.The sintering process of hot pressed gold diamond tool requires: temperature reaches 1000 ℃ ± 2 ℃, and forming pressure is 16～50MPa, and the heat-insulation pressure keeping time is 15～30min, and environment is antivacuum state.Under this working condition; Requirement has electroconductibility, higher resistivity, enough physical strength, good oxidization resistance ability and long work-ing life as the graphite jig of moulding and Heating element, reaches the work-ing life of length with this dimensional precision, excellent properties of guaranteeing the hot pressed gold diamond tool.
At present; Domestic high temperature hot pressing diamond tool is used graphite jig; Generally select for use common graphite or high purity graphite to process, through type selecting, development and improvement constantly, its main technical parameters can satisfy the requirement of its hot-pressing sintering technique basically; But compare with current international most advanced level, also have bigger gap.
The hot pressed gold diamond tool of developed countries such as Europe, U.S.A, day is used graphite jig, mainly is the graphite material of ultra-fine grain structure, high purity and high graphitization degree, require its median size less than 15 μ m, even below the 10 μ m, medium pore size is less than 2 μ m.The graphite jig of the high graphitization degree made from the carbon raw of ultra-fine grain; Has little, the compact structure of void content; Surface smoothness is high, resistance to compression, folding strength height, and resistivity is high; Oxidation-resistance is these characteristics by force, can guarantee dimensional precision, surface smoothness and the grinding performance of hot pressed gold diamond tool thus.
Because the raw-material super fine powder technology difficulty of carbon element is very big; At present; Have only developed countries such as Europe, U.S.A, day can produce the graphite jig of this ultra-fine grain structure, the carbon element particle of domestic production, median size can only reach 37～45 μ m; Indivedual manufacturers can reach 25 μ m, but can't produce in batches.Simultaneously, the high purity graphite of domestic production, its purity is also far below abroad, and graphite jig short texture, the particle produced thus are thicker, and mold surface finish is low, void content is high, and antioxidant property and ultimate compression strength are relatively low.Therefore; Present graphite jig is the following problem of ubiquity in use: (1) die surface oxidation rate is too fast; Because oxidation corrosion causes that die surface pore and surfaceness increase, outward appearance and dimensional precision reduce; Not only influence graphite jig work-ing life, and influence the diamond tool working accuracy.(2) mould is in the repeated use process, because oxidation corrosion intensity reduces, usually fracture appears in mould in hot pressing, and this not only causes the huge waste of graphite, has increased the diamond tool manufacturing cost simultaneously, has also brought the hidden danger on the production safety.(3) mould conduction, heat conductivility descend, and influence the inner quality and the stability thereof of diamond tool.Therefore, in the high temperature hot pressing,, have to limit the access times of graphite jig in order to ensure diamond tool quality of stability and production security.At present, domestic graphite jig access times are merely 1/4th of external product access times at 5～8 times, and this not only causes the huge waste of graphite material, has increased the manufacturing cost of diamond tool simultaneously.The hyperfine structure graphite jig mainly is to rely on import on the home market, and price is very high, is 4～5 times of domestic common graphite mould quotation.Therefore, make diamond tool to elevated temperature heat compacting and carry out anti-oxidant monographic study, select that a kind of technology is simple, cost is low, be easy to the antioxidation treatment technology of suitability for industrialized production, have very important significance with graphite jig.
In recent years, Chinese scholars has been carried out big quantity research to the graphite anti-oxidation tech, has researched and developed out multiple reduction graphite material oxidation consumption new technology, for example: antioxidation surface coating method, solution dipping method, self-healing and charcoal pottery composite algorithm etc.The anti-oxidant problem of graphite material below 1600 ℃ solves basically in air, but considers that from the over-all properties and the purposes of graphite material still have unsolved technical problem, various anti-oxidation treatment methods also have certain defective and limitation.Top coat method cost value is high, and the difference of thermal expansion coefficients between coating and the graphite matrix is big, in the high temperature hot pressing, is prone to come off or crack, and forms the diffusion admittance of oxygen, can reduce the antioxidant property of graphite jig; Self-healing and charcoal pottery composite algorithm; Be through being added on the ceramic particle oxidation in the graphite material matrix; Form ceramic membrane on the graphite material surface, make the surface of graphite material have some ceramic material properties, although improved the oxidation-resistance and the ultimate compression strength of graphite; But can cause the decline of graphite material electroconductibility, self lubricity reduction etc., make diamond tool for hot pressed sintering and be restricted with the graphite jig antioxidation treatment; Solution dipping method is to have porousness to graphite material; Select the extraordinary anti-oxidant soaker solution of preparation,, inhibitor is sealed to the pore of graphite material through certain treatment process; And form one deck protection against oxidation layer on the surface, stop the oxidation corrosion of oxidizing gas to graphite.Solution dipping method is less to the properties influence of graphite material, has kept the self-characteristic of graphite material after the processing basically, and shortcoming is that antioxidant effect is not so good as coating, self-healing and charcoal pottery composite algorithm.
Summary of the invention
The objective of the invention is to overcome the defective that present high temperature hot pressing diamond tool exists with graphite jig; Provide that a kind of technology is simple, cost is low, be applicable to the antioxidation treatment technology of thermal pressing sintering diamond tool with the pyrographite mould, i.e. the technical problem that the present invention will solve provides a kind of thermal pressing sintering diamond tool with the anti-oxidant soaker of graphite jig and compound method and treatment process.
In order to address the above problem, the technical scheme that the present invention adopts is:
The present invention provides a kind of thermal pressing sintering diamond tool with the anti-oxidant soaker of graphite jig; Said anti-oxidant soaker is formulated by composite phosphate, high temperature resistant solidifying agent, resistance to compression toughener, pH regulator agent and water; Said composite phosphate, high temperature resistant solidifying agent, resistance to compression toughener, pH regulator agent and the shared weight percentage of water are respectively 15～45%, 0.5～6%, 0.2～4%, 0.1～2% and the water of surplus, and each composition weight percentage sum is 100%.
With the anti-oxidant soaker of graphite jig, said composite phosphate is to be main with aluminium dihydrogen phosphate according to above-mentioned thermal pressing sintering diamond tool, adds any or two kinds in zn phosphate and the ammonium hydrogen phosphate;
Said high temperature resistant solidifying agent is an alkaline metal fluoride cpd;
Said resistance to compression toughener be in nitride, carbide and the oxide compound any or any two or three kinds; Perhaps said resistance to compression toughener is to be main with nitride, adds any or two kinds in carbide and the oxide compound;
Said pH regulator agent is an industrial phosphoric acid.(it is that 65% phosphoric acid or mass percentage concentration are 85% phosphoric acid that industrial phosphoric acid generally adopts mass percentage concentration).
With the anti-oxidant soaker of graphite jig, said composite phosphate is to be main with aluminium dihydrogen phosphate according to above-mentioned thermal pressing sintering diamond tool, adds zn phosphate, and the mass ratio of add-on is 3～1:1 between aluminium dihydrogen phosphate and the zn phosphate; Said composite phosphate is to be main with aluminium dihydrogen phosphate, adds ammonium hydrogen phosphate, and the mass ratio of add-on is 3～1:1 between aluminium dihydrogen phosphate and the ammonium hydrogen phosphate; Said composite phosphate is to be main with aluminium dihydrogen phosphate, adds zn phosphate and ammonium hydrogen phosphate, and the mass ratio of add-on is 3:1:1～1:1:1 between aluminium dihydrogen phosphate and zn phosphate, the ammonium hydrogen phosphate three;
Said alkaline metal fluoride cpd be in Sodium Fluoride, Potassium monofluoride and the Calcium Fluoride (Fluorspan) any or any two;
Said nitride is SP 1 or silicon nitride; Said carbide is charing boron or carborundum; Said oxide compound is boron trioxide or silicon-dioxide.
With the anti-oxidant soaker of graphite jig, said resistance to compression toughener is to be main with nitride according to above-mentioned thermal pressing sintering diamond tool, adds carbide, and during the two mixing of nitride and carbide, the shared weight percentage of nitride is 50～75%;
Said resistance to compression toughener is to be main with nitride, adds oxide compound, and during the two mixing of nitride and oxide compound, the shared weight percentage of nitride is 50～75%;
Said resistance to compression toughener is to be main with nitride; Add carbide and oxide compound; When nitride, carbide and oxide compound three mixed, the shared weight percentage of nitride was 50～75%, and the two weight percentage that accounts for altogether of carbide and oxide compound is 25～50%; When carbide and oxide compound were 25～50% blend according to the weight percentage that accounts for altogether, blending ratio was an arbitrary proportion.
With the anti-oxidant soaker of graphite jig, when said alkaline metal fluoride cpd was in Sodium Fluoride, Potassium monofluoride and the Calcium Fluoride (Fluorspan) any two, the mass ratio between two kinds of fluorochemicals was 1:1 according to above-mentioned thermal pressing sintering diamond tool.
A kind of compound method of above-mentioned anti-oxidant soaker, said compound method may further comprise the steps:
A, prepare various raw materials according to the proportioning ratio of above-mentioned anti-oxidant soaker; At first in composite phosphate, add entry; Constantly heating under the stirring condition, be heated to 65～80 ℃ and fully dissolve, under 65～80 ℃ of conditions, dissolve 0.5～1.5h; Fully obtain homogeneous transparent liquid after the dissolving, gained homogeneous transparent liquid is placed no crystalline polamer for a long time;
B, in the homogeneous transparent liquid that step a obtains, add high temperature resistant solidifying agent and resistance to compression toughener, it is even to continue heated and stirred, and temperature is controlled at 60～75 ℃ during heated and stirred, and the heated and stirred time is 0.5～1.0h;
Add the pH regulator agent in c, the last liquid after step b stirs, regulate pH value to 1～3 of mixing liquid, obtaining uniform and stable translucent suspension-s after the adjusting is anti-oxidant soaker solution.
According to the compound method of above-mentioned anti-oxidant soaker, in the said anti-oxidant soaker solution of step c with P
2O
5Meter, the shared quality percentage composition of total phosphate is controlled at 10～35%; Said anti-oxidant soaker solution 25 ℃, be coated with under-4 glasss the condition its Nian Du ≦ 30s.
A kind of method of utilizing above-mentioned anti-oxidant soaker to handle graphite jig the treating method comprises following steps:
A, at first graphite jig base appearance is carried out pre-treatment, said pre-treatment for clean successively, dry, calcination;
B, adopt anti-oxidant soaker solution to carry out dip treating the pretreated graphite jig of step a; The condition of dip treating is the vacuum pressed dipping, and impregnation pressure is 0.1～0.8MPa, and dipping temperature is 25～65 ℃; Vacuum tightness is-0.015MPa that time of immersion is 1.5～5.0h; Said anti-oxidant soaker solution is to utilize above-mentioned anti-oxidant soaker proportioning ratio formulated, and compound method is to adopt above-mentioned compound method;
C, thermal treatment: the graphite jig after the step b dip treating is cured, and solidification value is warming up to 900 ℃ by room temperature, is incubated 15～20 min after being warming up to 900 ℃; Solidify the back and adopt that stove is cold lowers the temperature, be cooled to room temperature.
The anti-oxidant soaker that utilizes according to above-mentioned is handled the method for graphite jig; Clean described in the step a is to adopt organic solvent industrial spirit or zero(ppm) water to soak; Being about to graphite jig base appearance is immersed in organic solvent or the zero(ppm) water; Soak time is 1.0～1.5h, removes in the graphite jig micropore after the cleaning and the greasy dirt dust on surface;
Said when dry drying temperature be 120～150 ℃, be dried to constant weight;
Said calcination adopts the energy-conservation box retort furnace of 4000W to carry out calcination; The control calcination temperature is 600～700 ℃, and calcination time is 30～40min., and the calcination postcooling is to room temperature; Remove the organism of graphite surface after the calcination; Adopt pressurized air to purge the graphite jig surface then, remove top layer discrete particle and dust, expose unoxidized graphite surface.
The anti-oxidant soaker that utilizes according to above-mentioned is handled the method for graphite jig, is warming up to 900 ℃ by room temperature described in the step c, and its heat-up rate is 4～6 ℃/min; The said room temperature that is cooled to, temperature fall time are 10～15h.
The present invention adopts solution dipping method antioxidation treatment technology; Disclose a kind of anti-oxidant impregnant composition to the thermal pressing sintering diamond tool manufacturing with graphite jig, graphite jig is carried out antioxidation treatment, the graphite jig after the antioxidation treatment with this compsn; The basic electrology characteristic that keeps graphite material self; Satisfying fully under the thermal pressing sintering diamond tool manufacture process requirement situation, improving the oxidation-resistance and the ultimate compression strength of graphite jig, prolonging the work-ing life of graphite jig.
Positive beneficial effect of the present invention:
1, utilizes the anti-oxidant soaker solution of the present invention; Under certain process requires, thermal pressing sintering diamond tool is carried out antioxidation treatment with graphite jig, the graphite jig after the processing; Basically the electrology characteristic that has kept graphite material self, resistivity are not more than 20 Ω mm
2/ m, void content has reduced by 50%
,In not oxidation basically below 800 ℃, ultimate compression strength obviously improves
The anti-oxidant soaker of the present invention also can be used for the anti-oxidant dip treating of various graphite materials, and its antioxidation treatment effect is superior to similar products at home and abroad.
2, the present invention adopts the anti-oxidant soaker of different proportionings; Its graphite jig is carried out dip treating; Handling the back tests its graphite jig; And with utilize graphite jig after existing soaker is handled to detect data to compare, the influence of the soaker of heterogeneity to the oxidation-resistance and the ultimate compression strength of graphite jig is described with this, test result sees table 1 for details.
Table 1 heterogeneity soaker is to the influence of graphite jig oxidation-resistance and ultimate compression strength
Indicate: the proportioning of anti-oxidant soaker is formed and is seen embodiment 1, compound method for details and see embodiment 9 for details, the dip treating method of graphite jig is seen for details embodiment 13 in the technical scheme 1 of the present invention; The proportioning of anti-oxidant soaker is formed and to be seen embodiment 2, compound method for details and see embodiment 9 for details, the dip treating method of graphite jig is seen for details embodiment 13 in the technical scheme 2 of the present invention; The proportioning of anti-oxidant soaker is formed and to be seen embodiment 3, compound method for details and see embodiment 9 for details, the dip treating method of graphite jig is seen for details embodiment 13 in the technical scheme 3 of the present invention.
3, can know by above-mentioned table 1 test-results, adopt the solution dipping method treatment technology, and utilize the compsn of the anti-oxidant soaker of the present invention; Graphite jig is carried out anti-oxidant dip treating; Graphite jig after the processing, antioxidant property is better, and ultimate compression strength is significantly improved.
4, utilize technical scheme of the present invention that graphite jig is carried out anti-oxidant dip treating, the graphite jig sample after the dip treating is carried out correlation detection, its resistivity is not more than 20 Ω mm
2/ m, void content has reduced by 50%, and graphite jig is in diamond high speed, ultra-thin parting tool manufacturing are used, and is respond well, satisfies the hot-pressing sintering technique requirement fully; Sintering temperature is in the time of 600～900 ℃, and mean life handled preceding the use 5～8 times by graphite jig, uses 16～20 times after the anti-oxidant dip treating of the present invention.
5, visible by anti-oxidant dipping experiment of table 1 and product practical application; The anti-oxidant soaker of the present invention is a kind of anti-oxidant material of excellent property; This soaker can be used for the anti-oxidant dip treating process of various graphite materials, is specially adapted to the anti-oxidant dip treating of thermal pressing sintering diamond tool with graphite jig, the graphite jig after the processing; Basic graphite material self electrology characteristic that keeps; Antioxidant property is good, and ultimate compression strength obviously improves, and its antioxidation treatment effect is superior to similar products at home and abroad.
Four, embodiment:
Following examples have been merely and have further specified the present invention, do not limit content of the present invention.
Embodiment 1:
A kind of thermal pressing sintering diamond tool is with the anti-oxidant soaker of graphite jig; Said anti-oxidant soaker is formulated by composite phosphate, high temperature resistant solidifying agent, resistance to compression toughener, pH regulator agent and water; Said composite phosphate, high temperature resistant solidifying agent, resistance to compression toughener, pH regulator agent and the shared weight percentage of water are respectively 30%, 3%, 2%, 0.8% and the water of surplus, and each composition weight percentage sum is 100%.
Said composite phosphate is to be main with aluminium dihydrogen phosphate, adds zn phosphate and ammonium hydrogen phosphate, and the mass ratio of add-on is 3:1:1 between aluminium dihydrogen phosphate and zn phosphate, the ammonium hydrogen phosphate three;
Said high temperature resistant solidifying agent is a Sodium Fluoride; Said resistance to compression toughener is a SP 1; Said pH regulator agent is that mass percentage concentration is 85% industrial phosphoric acid.
Embodiment 2: basic identical with embodiment 1, difference is:
Said composite phosphate, high temperature resistant solidifying agent, resistance to compression toughener, pH regulator agent and the shared weight percentage of water are respectively 20%, 2.5%, 1.5%, 1.2% and the water of surplus, and each composition weight percentage sum is 100%.
Said composite phosphate is to be main with aluminium dihydrogen phosphate, adds zn phosphate, and the mass ratio of add-on is 3:1 between aluminium dihydrogen phosphate and the zn phosphate; Said high temperature resistant solidifying agent is a Potassium monofluoride; Said resistance to compression toughener is a charing boron.
Embodiment 3: basic identical with embodiment 1, difference is:
Said composite phosphate, high temperature resistant solidifying agent, resistance to compression toughener, pH regulator agent and the shared weight percentage of water are respectively 40%, 5%, 1%, 0.3% and the water of surplus, and each composition weight percentage sum is 100%.
Said composite phosphate is to be main with aluminium dihydrogen phosphate, adds ammonium hydrogen phosphate, and the mass ratio of add-on is 3:1 between aluminium dihydrogen phosphate and the ammonium hydrogen phosphate; Said high temperature resistant solidifying agent is a Calcium Fluoride (Fluorspan); Said resistance to compression toughener is a boron trioxide.
Embodiment 4: basic identical with embodiment 1, difference is:
Said composite phosphate, high temperature resistant solidifying agent, resistance to compression toughener, pH regulator agent and the shared weight percentage of water are respectively 45%, 2%, 3%, 0.2% and the water of surplus, and each composition weight percentage sum is 100%.
Said composite phosphate is to be main with aluminium dihydrogen phosphate, adds zn phosphate and ammonium hydrogen phosphate, and the mass ratio of add-on is 2:1:1 between aluminium dihydrogen phosphate and zn phosphate, the ammonium hydrogen phosphate three; Said high temperature resistant solidifying agent is the mixture of Sodium Fluoride and Potassium monofluoride, and the mixing quality of the two is than being 1:1; Said resistance to compression toughener is the mixture of silicon nitride and carborundum, and the shared weight percentage of silicon nitride was 70% when the two mixed.
Embodiment 5: basic identical with embodiment 1, difference is:
Said composite phosphate, high temperature resistant solidifying agent, resistance to compression toughener, pH regulator agent and the shared weight percentage of water are respectively 15%, 0.5%, 0.2%, 2% and the water of surplus, and each composition weight percentage sum is 100%.
Said composite phosphate is to be main with aluminium dihydrogen phosphate, adds zn phosphate and ammonium hydrogen phosphate, and the mass ratio of add-on is 1:1:1 between aluminium dihydrogen phosphate and zn phosphate, the ammonium hydrogen phosphate three; Said high temperature resistant solidifying agent is the mixture of Sodium Fluoride and Calcium Fluoride (Fluorspan), and the mixing quality of the two is than being 1:1; Said resistance to compression toughener is the mixture of silicon nitride and silicon-dioxide, and the shared weight percentage of silicon nitride was 75% when the two mixed.
Embodiment 6: basic identical with embodiment 1, difference is:
Said composite phosphate, high temperature resistant solidifying agent, resistance to compression toughener, pH regulator agent and the shared weight percentage of water are respectively 25%, 1.5%, 1.2%, 0.5% and the water of surplus, and each composition weight percentage sum is 100%.
Said composite phosphate is to be main with aluminium dihydrogen phosphate, adds zn phosphate, and the mass ratio of add-on is 2:1 between aluminium dihydrogen phosphate and the zn phosphate; Said high temperature resistant solidifying agent is a Sodium Fluoride; Said resistance to compression toughener is the mixture of SP 1 and charing boron, and the shared weight percentage of SP 1 was 65% when the two mixed.
Embodiment 7: basic identical with embodiment 1, difference is:
Said composite phosphate, high temperature resistant solidifying agent, resistance to compression toughener, pH regulator agent and the shared weight percentage of water are respectively 35%, 4.5%, 3.5%, 0.5% and the water of surplus, and each composition weight percentage sum is 100%.
Said composite phosphate is to be main with aluminium dihydrogen phosphate, adds zn phosphate, and the mass ratio of add-on is 1:1 between aluminium dihydrogen phosphate and the zn phosphate; Said high temperature resistant solidifying agent is a Sodium Fluoride; Said resistance to compression toughener is the mixture of SP 1 and boron trioxide, and the shared weight percentage of SP 1 was 60% when the two mixed.
Embodiment 8: basic identical with embodiment 1, difference is:
Said composite phosphate, high temperature resistant solidifying agent, resistance to compression toughener, pH regulator agent and the shared weight percentage of water are respectively 42%, 6%, 4%, 0.6% and the water of surplus, and each composition weight percentage sum is 100%.
Said composite phosphate is to be main with aluminium dihydrogen phosphate, adds ammonium hydrogen phosphate, and the mass ratio of add-on is 2:1 between aluminium dihydrogen phosphate and the ammonium hydrogen phosphate; Said high temperature resistant solidifying agent is a Calcium Fluoride (Fluorspan); Said resistance to compression toughener is SP 1 and charing boron, boron trioxide three's a mixture, and SP 1, charing boron and the shared weight percentage of boron trioxide were respectively 55%, 30% and 15% when the three mixed.
Embodiment 9:
A kind of compound method of anti-oxidant soaker, the detailed step of said compound method is following:
A, prepare various raw materials according to the proportioning ratio of anti-oxidant dipping described in the embodiment 1; At first in composite phosphate, add entry; Constantly heating under the stirring condition, be heated to 70 ℃ and fully dissolve, under 70 ℃ of conditions, dissolve 1h; Fully obtain homogeneous transparent liquid after the dissolving, gained homogeneous transparent liquid is placed no crystalline polamer for a long time;
B, in the homogeneous transparent liquid that step a obtains, add high temperature resistant solidifying agent and resistance to compression toughener, it is even to continue heated and stirred, and temperature is controlled at 70 ℃ during heated and stirred, and the heated and stirred time is 1.0h;
Add the pH regulator agent in c, the last liquid after step b stirs, regulate pH value to 1～3 of mixing liquid, obtain uniform and stable translucent suspension-s after the adjusting and be anti-oxidant soaker solution (in the anti-oxidant soaker solution with P
2O
5Meter, the shared quality percentage composition of total phosphate is controlled at 10～35%; Said anti-oxidant soaker solution 25 ℃, be coated with under-4 glasss the condition its Nian Du ≦ 30s).
Embodiment 10: basic identical with embodiment 9, difference is:
Among the step a: the proportioning ratio according to anti-oxidant dipping described in the embodiment 2 is prepared various raw materials, is heated to 80 ℃ and fully dissolves, and under 80 ℃ of conditions, dissolves 0.5h;
Among the step b: temperature is controlled at 75 ℃ during heated and stirred, and the heated and stirred time is 0.5h.
Embodiment 11: basic identical with embodiment 9, difference is:
Among the step a: the proportioning ratio according to anti-oxidant dipping described in the embodiment 3 is prepared various raw materials, is heated to 65 ℃ and fully dissolves, and under 65 ℃ of conditions, dissolves 1.5h;
Among the step b: temperature is controlled at 60 ℃ during heated and stirred, and the heated and stirred time is 1.0h.
Embodiment 12: basic identical with embodiment 9, difference is:
Among the step a: the proportioning ratio according to anti-oxidant dipping described in the embodiment 6 is prepared various raw materials, is heated to 75 ℃ and fully dissolves, and under 75 ℃ of conditions, dissolves 1.0h;
Among the step b: temperature is controlled at 65 ℃ during heated and stirred, and the heated and stirred time is 1.0h.
Embodiment 13:
A kind of method of utilizing anti-oxidant soaker to handle graphite jig of the present invention the treating method comprises following steps:
A, at first graphite jig base appearance is carried out pre-treatment, said pre-treatment for clean successively, dry, calcination;
Said cleaning is to adopt industrial spirit or zero(ppm) water to soak, and is about to graphite jig base appearance and is immersed in organic solvent or the zero(ppm) water, and soak time is 1.0～1.5h, removes in the graphite jig micropore after the cleaning and the greasy dirt dust on surface;
Said when dry drying temperature be 130 ℃, be dried to constant weight;
Said calcination adopts the energy-conservation box retort furnace of 4000W to carry out calcination; The control calcination temperature is 650 ℃, and calcination time is 35min, and the calcination postcooling is to room temperature; Remove the organism of graphite surface after the calcination; Adopt pressurized air to purge the graphite jig surface then, remove top layer discrete particle and dust, expose unoxidized graphite surface;
B, adopt anti-oxidant soaker solution to carry out dip treating the pretreated graphite jig of step a, the condition of dip treating is the vacuum pressed dipping, and impregnation pressure is 0.5MPa, and dipping temperature is 45 ℃, and vacuum tightness is-0.015MPa that time of immersion is 3.0h; Said anti-oxidant soaker solution is to utilize embodiment 1 described anti-oxidant soaker proportioning ratio formulated, and compound method is to adopt the compound method of embodiment 9;
C, thermal treatment: the graphite jig after the step b dip treating is cured, solidification value by room temperature be warming up to 900 ℃ (its heat-up rate be 4～6 ℃/min), be incubated 15～20 min after being warming up to 900 ℃; Solidify the back and adopt that stove is cold lowers the temperature, (temperature fall time is 10～15h) to be cooled to room temperature.
Graphite jig to after the dip treating is tested.
Embodiment 14: basic identical with embodiment 13, difference is:
Step a: said when dry drying temperature be 120 ℃; The control calcination temperature is 600 ℃, and calcination time is 40min;
Step b: the condition of dip treating is the vacuum pressed dipping, and impregnation pressure is 0.8MPa, and dipping temperature is 25 ℃, and vacuum tightness is-0.015MPa that time of immersion is 4.0h; Said anti-oxidant soaker solution is to utilize embodiment 2 described anti-oxidant soaker proportioning ratios formulated, and compound method is to adopt the compound method of embodiment 9.
Embodiment 15: basic identical with embodiment 13, difference is:
Step a: said when dry drying temperature be 150 ℃; The control calcination temperature is 700 ℃, and calcination time is 30min;
Step b: the condition of dip treating is the vacuum pressed dipping, and impregnation pressure is 0.3MPa, and dipping temperature is 60 ℃, and vacuum tightness is-0.015MPa that time of immersion is 2.0h; Said anti-oxidant soaker solution is to utilize embodiment 3 described anti-oxidant soaker proportioning ratios formulated, and compound method is to adopt the compound method of embodiment 9.
Claims (10)
1. a thermal pressing sintering diamond tool is with the anti-oxidant soaker of graphite jig; It is characterized in that: said anti-oxidant soaker is formulated by composite phosphate, high temperature resistant solidifying agent, resistance to compression toughener, pH regulator agent and water; Said composite phosphate, high temperature resistant solidifying agent, resistance to compression toughener, pH regulator agent and the shared weight percentage of water are respectively 15～45%, 0.5～6%, 0.2～4%, 0.1～2% and the water of surplus, and each composition weight percentage sum is 100%.
2. thermal pressing sintering diamond tool according to claim 1 is characterized in that with the anti-oxidant soaker of graphite jig: said composite phosphate is to be main with aluminium dihydrogen phosphate, adds any or two kinds in zn phosphate and the ammonium hydrogen phosphate;
Said high temperature resistant solidifying agent is an alkaline metal fluoride cpd;
Said resistance to compression toughener be in nitride, carbide and the oxide compound any or any two or three kinds; Perhaps said resistance to compression toughener is to be main with nitride, adds any or two kinds in carbide and the oxide compound;
Said pH regulator agent is an industrial phosphoric acid.
3. thermal pressing sintering diamond tool according to claim 2 is with the anti-oxidant soaker of graphite jig; It is characterized in that: said composite phosphate is to be main with aluminium dihydrogen phosphate; Add zn phosphate, the mass ratio of add-on is 3～1:1 between aluminium dihydrogen phosphate and the zn phosphate; Said composite phosphate is to be main with aluminium dihydrogen phosphate, adds ammonium hydrogen phosphate, and the mass ratio of add-on is 3～1:1 between aluminium dihydrogen phosphate and the ammonium hydrogen phosphate; Said composite phosphate is to be main with aluminium dihydrogen phosphate, adds zn phosphate and ammonium hydrogen phosphate, and the mass ratio of add-on is 3:1:1～1:1:1 between aluminium dihydrogen phosphate and zn phosphate, the ammonium hydrogen phosphate three;
Said alkaline metal fluoride cpd be in Sodium Fluoride, Potassium monofluoride and the Calcium Fluoride (Fluorspan) any or any two;
Said nitride is SP 1 or silicon nitride; Said carbide is charing boron or carborundum; Said oxide compound is boron trioxide or silicon-dioxide.
4. thermal pressing sintering diamond tool according to claim 2 is with the anti-oxidant soaker of graphite jig; It is characterized in that: said resistance to compression toughener is to be main with nitride; Add carbide, during the two mixing of nitride and carbide, the shared weight percentage of nitride is 50～75%;
Said resistance to compression toughener is to be main with nitride, adds oxide compound, and during the two mixing of nitride and oxide compound, the shared weight percentage of nitride is 50～75%;
Said resistance to compression toughener is to be main with nitride; Add carbide and oxide compound; When nitride, carbide and oxide compound three mixed, the shared weight percentage of nitride was 50～75%, and the two weight percentage that accounts for altogether of carbide and oxide compound is 25～50%; When carbide and oxide compound were 25～50% blend according to the weight percentage that accounts for altogether, blending ratio was an arbitrary proportion.
5. thermal pressing sintering diamond tool according to claim 3 is characterized in that with the anti-oxidant soaker of graphite jig: when said alkaline metal fluoride cpd was in Sodium Fluoride, Potassium monofluoride and the Calcium Fluoride (Fluorspan) any two, the mass ratio between two kinds of fluorochemicals was 1:1.
6. the compound method of the described anti-oxidant soaker of claim 1 is characterized in that, said compound method may further comprise the steps:
A, prepare various raw materials according to the proportioning ratio of the said anti-oxidant soaker of claim 1; At first in composite phosphate, add entry; Constantly heating under the stirring condition, be heated to 65～80 ℃ and fully dissolve, under 65～80 ℃ of conditions, dissolve 0.5～1.5h; Fully obtain homogeneous transparent liquid after the dissolving, gained homogeneous transparent liquid is placed no crystalline polamer for a long time;
B, in the homogeneous transparent liquid that step a obtains, add high temperature resistant solidifying agent and resistance to compression toughener, it is even to continue heated and stirred, and temperature is controlled at 60～75 ℃ during heated and stirred, and the heated and stirred time is 0.5～1.0h;
Add the pH regulator agent in c, the last liquid after step b stirs, regulate pH value to 1～3 of mixing liquid, obtaining uniform and stable translucent suspension-s after the adjusting is anti-oxidant soaker solution.
7. the compound method of anti-oxidant soaker according to claim 6 is characterized in that: in the said anti-oxidant soaker solution of step c with P
2O
5Meter, the shared quality percentage composition of total phosphate is controlled at 10～35%; Said anti-oxidant soaker solution 25 ℃, be coated with under-4 glasss the condition its Nian Du ≦ 30s.
8. a method of utilizing the described anti-oxidant soaker of claim 1 to handle graphite jig is characterized in that, the treating method comprises following steps:
A, at first graphite jig base appearance is carried out pre-treatment, said pre-treatment for clean successively, dry, calcination;
B, adopt anti-oxidant soaker solution to carry out dip treating the pretreated graphite jig of step a; The condition of dip treating is the vacuum pressed dipping, and impregnation pressure is 0.1～0.8MPa, and dipping temperature is 25～65 ℃; Vacuum tightness is-0.015MPa that time of immersion is 1.5～5.0h; Said anti-oxidant soaker solution is to utilize the proportioning ratio of the said anti-oxidant soaker of claim 1 formulated, and compound method is to adopt the described compound method of claim 6;
C, thermal treatment: the graphite jig after the step b dip treating is cured, and solidification value is warming up to 900 ℃ by room temperature, is incubated 15～20 min after being warming up to 900 ℃; Solidify the back and adopt that stove is cold lowers the temperature, be cooled to room temperature.
9. the method for utilizing anti-oxidant soaker to handle graphite jig according to claim 8; It is characterized in that; Clean described in the step a is to adopt organic solvent industrial spirit or zero(ppm) water to soak; Be about to graphite jig base appearance and be immersed in organic solvent or the zero(ppm) water, soak time is 1.0～1.5h, removes in the graphite jig micropore after the cleaning and the greasy dirt dust on surface;
Said when dry drying temperature be 120～150 ℃, be dried to constant weight;
Said calcination adopts the energy-conservation box retort furnace of 4000W to carry out calcination; The control calcination temperature is 600～700 ℃, and calcination time is 30～40min., and the calcination postcooling is to room temperature; Remove the organism of graphite surface after the calcination; Adopt pressurized air to purge the graphite jig surface then, remove top layer discrete particle and dust, expose unoxidized graphite surface.
10. the method for utilizing anti-oxidant soaker to handle graphite jig according to claim 8, it is characterized in that: be warming up to 900 ℃ by room temperature described in the step c, its heat-up rate is 4～6 ℃/min; The said room temperature that is cooled to, temperature fall time are 10～15h.
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