CN104788792A - Method for preparing high-energy and low-temperature ball-milled and continuously-extruded composite and composite prepared by using method - Google Patents
Method for preparing high-energy and low-temperature ball-milled and continuously-extruded composite and composite prepared by using method Download PDFInfo
- Publication number
- CN104788792A CN104788792A CN201510238027.9A CN201510238027A CN104788792A CN 104788792 A CN104788792 A CN 104788792A CN 201510238027 A CN201510238027 A CN 201510238027A CN 104788792 A CN104788792 A CN 104788792A
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- CN
- China
- Prior art keywords
- matrix material
- ball milling
- potassium titanate
- crystal whisker
- low temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
- B02C17/10—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls with one or a few disintegrating members arranged in the container
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/068—Ultra high molecular weight polyethylene
Abstract
The invention discloses a method for preparing a high-energy and low-temperature ball-milled and continuously-extruded composite. The method comprises the following steps of (1) preparing a modified potassium hexatitanate whisker; (2) preparing composite filler, namely uniformly mixing the modified potassium hexatitanate whisker and polyformaldehyde, then, placing the mixture into a high-energy ball milling tank body, and carrying out ball milling at the temperature ranging from 150 DEG C below zero to 50 DEG C below zero after vacuumizing to obtain the composite filler, wherein the mass ratio of the modified potassium hexatitanate whisker to polyformaldehyde is (1-10):(9-30); and (3) preparing the composite, namely uniformly mixing ultra-high molecular weight polyethylene and the composite filler on a high-speed mixer, and continuously extruding the composite on a continuous extruding device, wherein the mass ratio of the ultra-high molecular weight polyethylene to the composite filler is (10-7):1. The invention also discloses the composite prepared by using the method. The nano-processing of a continuous extruding technology is realized, the raw material selecting range of the existing continuous extruding technology is widened, and the method can be used for developing a novel high-performance metal-based and polymer-based composite.
Description
Technical field
The present invention relates to a kind of method and the matrix material thereof of preparing matrix material, specifically a kind of prepare the continuously extruded matrix material of high energy low temperature ball milling method and the matrix material prepared of the method.
Background technology
Mechanical alloying is succeeded in developing when nineteen sixty-eight studies oxide compound enhancing nickel base superalloy by J.S.Benjamin and co-worker thereof at first.As one of important Mechanic Alloying Technology, within 1988, high-energy ball-milling process is introduced into polymer arts.In order to overcome viscous-elastic behaviour and the temperature sensitivity of polymer materials, in polymkeric substance Process During High Energy Ball Milling, adopt cooling working medium make polymkeric substance brittle and be easy to pulverize, this high-energy ball milling carried out under cryogenic is low temperature ball milling.
Since continual extruding technology was born from 1972, nearly more than 40 years.Global scope is seen, its Application Areas is only limitted to nonferrous materials plastic making.From the angle of the materialist dialectics, " change " is intramundane build-in attribute.Comply with the requirement of the materialist dialectics, continual extruding technology must seek new breakthrough! For continual extruding technology, process raw-material change and will cause a series of changes in aspect such as continuously extruded theory, Processes and apparatus.
At present, the non-ferrous metal raw material that in world wide, continual extruding technology is applied is all alloy or pure metal that metal melting process of setting occurred, not yet realizes the nanometer processing of material.The present invention is based on above present situation in continual extruding technology, introduce high energy low temperature ball milling, continuously extruded in order to realize nanometer just, can develop advanced metal matrix and polymer-based composite by the present invention, the original technological innovation for China is made major contribution by this.
Summary of the invention
According to the technical problem of above-mentioned proposition, and provide a kind of prepare the continuously extruded matrix material of high energy low temperature ball milling method and the matrix material prepared of the method.The technique means that the present invention adopts is as follows:
Prepare a method for the continuously extruded matrix material of high energy low temperature ball milling, there are following steps:
1) modification crystal whisker of hexa potassium titanate is prepared:
Dehydrated alcohol and deionized water are made into ethanol/water solution, and silane coupling agent is added in ethanol/water solution, obtain mixing solutions, pour mixing solutions into three-necked flask and stir, in three-necked flask, pour crystal whisker of hexa potassium titanate into afterwards and stir, silane coupling agent and crystal whisker of hexa potassium titanate mass ratio are 1 ~ 15:100, after reaction terminates, product is vacuum filtration, washing, vacuum-drying while hot, obtains modification crystal whisker of hexa potassium titanate stand-by after cooling;
As preferably, silane coupling agent and crystal whisker of hexa potassium titanate mass ratio are 2 ~ 7:100;
2) compounded mix is prepared:
Load high-energy ball milling tank body by after modification crystal whisker of hexa potassium titanate and polyoxymethylene Homogeneous phase mixing, the mass ratio of modification crystal whisker of hexa potassium titanate and polyoxymethylene is 1 ~ 10:9 ~ 30, and after vacuumizing, at the temperature of-150 ~-50 DEG C, ball milling prepares compounded mix;
As preferably, load high-energy ball milling tank body by after modification crystal whisker of hexa potassium titanate and polyoxymethylene Homogeneous phase mixing, the mass ratio of modification crystal whisker of hexa potassium titanate and polyoxymethylene is 1 ~ 10:9 ~ 30, and after vacuumizing, at the temperature of-100 ~-50 DEG C, ball milling prepares compounded mix;
3) matrix material is prepared:
Ultrahigh molecular weight polyethylene(UHMWPE) and compounded mix are mixed on high-speed mixer, continuous extrusion device extrudes matrix material continuously, wherein the mass ratio of ultrahigh molecular weight polyethylene(UHMWPE) and compounded mix is 10 ~ 7:1.
Step 1) in dehydrated alcohol, volume ratio between deionized water and silane coupling agent be 60 ~ 80:5 ~ 10:2 ~ 15, step 1) in silane coupling agent be A-1100 silane coupling agent.
Step 1) in three-necked flask, pour crystal whisker of hexa potassium titanate into and stir, churning time is 1 ~ 3h.
Step 1) in vacuum drying vacuum tightness be 1 ~ 9 × 10
-9pa.
As preferably, step 1) in vacuum drying vacuum tightness be 1 ~ 4 × 10
-9pa.
Step 2) in vacuumize after vacuum tightness be 1 ~ 8 × 10
-10pa.
As preferably, step 2) in vacuumize after vacuum tightness be 1 ~ 4 × 10
-10pa.
Step 2) in the ball milling Ball-milling Time of preparing compounded mix be 1 ~ 3h, the mass ratio of the compound of mill ball and modification crystal whisker of hexa potassium titanate and polyoxymethylene is 20 ~ 45:1, rotational speed of ball-mill 200 ~ 300r/min, mill ball is zirconia ball, diameter is 0.1 ~ 10mm, and compound refers to the mixture of modification crystal whisker of hexa potassium titanate and polyoxymethylene.
As preferably, step 2) in the ball milling Ball-milling Time of preparing compounded mix be 2h, the mass ratio of the compound of mill ball and modification crystal whisker of hexa potassium titanate and polyoxymethylene is 30:1, rotational speed of ball-mill 200 ~ 300r/min, mill ball is zirconia ball, diameter is 0.1 ~ 10mm, and compound refers to the mixture of modification crystal whisker of hexa potassium titanate and polyoxymethylene.
The molecular weight of ultrahigh molecular weight polyethylene(UHMWPE) is 100 ~ 1,000 ten thousand.
The diameter of crystal whisker of hexa potassium titanate 0.1 ~ 0.7 μm, length is 0.3 ~ 5 μm.
The molecular weight of polyoxymethylene is 10 ~ 200,000.
The invention also discloses a kind of matrix material prepared by aforesaid method.
The present invention has the following advantages:
1, the nanometer processing of continual extruding technology is realized;
2, the raw material selection range of existing continual extruding technology is expanded;
3, may be used for exploitation high-performance metal base and polymer-based composite material.
The present invention extensively can promote in fields such as preparing matrix material for the foregoing reasons.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the present invention is further detailed explanation.
Fig. 1 is DSC curve comparison diagram between each sample in the specific embodiment of the present invention.
Fig. 2 is the SEM figure of matrix material prepared by compression molding.
Fig. 3 is the SEM figure of a kind of matrix material prepared by a kind of method preparing the continuously extruded matrix material of high energy low temperature ball milling in the specific embodiment of the present invention.
Embodiment
Prepare a method for the continuously extruded matrix material of high energy low temperature ball milling, there are following steps:
1) modification crystal whisker of hexa potassium titanate is prepared:
Dehydrated alcohol and deionized water are made into ethanol/water solution, and silane coupling agent is added in ethanol/water solution, obtain mixing solutions, dehydrated alcohol, volume ratio between deionized water and silane coupling agent is 75:8:8, silane coupling agent is A-1100 silane coupling agent, pour mixing solutions into three-necked flask and stir, in three-necked flask, pour crystal whisker of hexa potassium titanate into afterwards and stir, churning time is 1 ~ 3h, silane coupling agent and crystal whisker of hexa potassium titanate mass ratio are 3:100, after reaction terminates, product is vacuum filtration while hot, washing, vacuum-drying, vacuum tightness is 2 × 10
-9pa,
Modification crystal whisker of hexa potassium titanate is obtained stand-by after cooling;
2) compounded mix is prepared:
Load high-energy ball milling tank body by after modification crystal whisker of hexa potassium titanate and polyoxymethylene Homogeneous phase mixing, the mass ratio of modification crystal whisker of hexa potassium titanate and polyoxymethylene is 1:15, and after vacuumizing, vacuum tightness is 2 × 10
-10pa, at the temperature of-92 DEG C, ball milling prepares compounded mix, and Ball-milling Time is 2h, and the mass ratio of the compound of mill ball and modification crystal whisker of hexa potassium titanate and polyoxymethylene is 30:1, rotational speed of ball-mill 300r/min, and mill ball is zirconia ball, and diameter is 5mm;
3) matrix material is prepared:
Ultrahigh molecular weight polyethylene(UHMWPE) and compounded mix are mixed on high-speed mixer, continuous extrusion device extrudes matrix material continuously, wherein the mass ratio of ultrahigh molecular weight polyethylene(UHMWPE) and compounded mix is 10 ~ 7:1, continuous extrusion device is the continuously extruded experimental installation ZL201210105481.3 of visual ultrahigh molecular weight polyethylene(UHMWPE), extrusion temperature is 150-210 DEG C, extrusion speed 20 ~ 90mm/min.
The molecular weight of ultrahigh molecular weight polyethylene(UHMWPE) is 100 ~ 1,000 ten thousand.
The diameter of crystal whisker of hexa potassium titanate 0.1 ~ 0.7 μm, length is 0.3 ~ 5 μm.
The molecular weight of polyoxymethylene is 10 ~ 200,000.
The matrix material prepared by aforesaid method comprises sample 2, sample 3, sample 4, sample 5,
The ultrahigh molecular weight polyethylene(UHMWPE) of sample 2 and the mass ratio of compounded mix are 10:1,
The ultrahigh molecular weight polyethylene(UHMWPE) of sample 3 and the mass ratio of compounded mix are 9:1,
The ultrahigh molecular weight polyethylene(UHMWPE) of sample 4 and the mass ratio of compounded mix are 8:1,
The ultrahigh molecular weight polyethylene(UHMWPE) of sample 5 and the mass ratio of compounded mix are 7:1,
Sample 1 is pure ultra-high molecular mass polyethylene,
As shown in Figure 1, sample 2 ~ 5 is compared with sample 1, and fusing point increases.
As shown in Figures 2 and 3, compared with the matrix material prepared with compression molding, the molecular orientation of sample 3 increases.
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (10)
1. prepare a method for the continuously extruded matrix material of high energy low temperature ball milling, it is characterized in that there are following steps:
1) modification crystal whisker of hexa potassium titanate is prepared:
Dehydrated alcohol and deionized water are made into ethanol/water solution, and silane coupling agent is added in ethanol/water solution, obtain mixing solutions, pour mixing solutions into three-necked flask and stir, in three-necked flask, pour crystal whisker of hexa potassium titanate into afterwards and stir, silane coupling agent and crystal whisker of hexa potassium titanate mass ratio are 1 ~ 15:100, after reaction terminates, product is vacuum filtration, washing, vacuum-drying while hot, obtains modification crystal whisker of hexa potassium titanate stand-by after cooling;
2) compounded mix is prepared:
Load high-energy ball milling tank body by after modification crystal whisker of hexa potassium titanate and polyoxymethylene Homogeneous phase mixing, the mass ratio of modification crystal whisker of hexa potassium titanate and polyoxymethylene is 1 ~ 10:9 ~ 30, and after vacuumizing, at the temperature of-150 ~-50 DEG C, ball milling prepares compounded mix;
3) matrix material is prepared:
Ultrahigh molecular weight polyethylene(UHMWPE) and compounded mix are mixed on high-speed mixer, continuous extrusion device extrudes matrix material continuously, wherein the mass ratio of ultrahigh molecular weight polyethylene(UHMWPE) and compounded mix is 10 ~ 7:1.
2. a kind of method preparing the continuously extruded matrix material of high energy low temperature ball milling according to claim 1, it is characterized in that: step 1) in dehydrated alcohol, volume ratio between deionized water and silane coupling agent be 60 ~ 80:5 ~ 10:2 ~ 15, step 1) in silane coupling agent be A-1100 silane coupling agent.
3. a kind of method preparing the continuously extruded matrix material of high energy low temperature ball milling according to claim 1, is characterized in that: step 1) in three-necked flask, pour crystal whisker of hexa potassium titanate into and stir, churning time is 1 ~ 3h.
4. a kind of method preparing the continuously extruded matrix material of high energy low temperature ball milling according to claim 1, is characterized in that: step 1) in vacuum drying vacuum tightness be 1 ~ 9 × 10
-9pa.
5. a kind of method preparing the continuously extruded matrix material of high energy low temperature ball milling according to claim 1, is characterized in that: step 2) in vacuumize after vacuum tightness be 1 ~ 8 × 10
-10pa.
6. a kind of method preparing the continuously extruded matrix material of high energy low temperature ball milling according to claim 1, it is characterized in that: step 2) in the ball milling Ball-milling Time of preparing compounded mix be 1 ~ 3h, the mass ratio of the compound of mill ball and modification crystal whisker of hexa potassium titanate and polyoxymethylene is 20 ~ 45:1, rotational speed of ball-mill 200 ~ 300r/min, mill ball is zirconia ball, and diameter is 0.1 ~ 10mm.
7. a kind of method preparing the continuously extruded matrix material of high energy low temperature ball milling according to claim 1, is characterized in that: the molecular weight of ultrahigh molecular weight polyethylene(UHMWPE) is 100 ~ 1,000 ten thousand.
8. a kind of method preparing the continuously extruded matrix material of high energy low temperature ball milling according to claim 1, it is characterized in that: the diameter of crystal whisker of hexa potassium titanate 0.1 ~ 0.7 μm, length is 0.3 ~ 5 μm.
9. a kind of method preparing the continuously extruded matrix material of high energy low temperature ball milling according to claim 1, is characterized in that: the molecular weight of polyoxymethylene is 10 ~ 200,000.
10. the matrix material prepared by the method described in claim 1-9 any one.
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|---|---|---|---|
| CN201510238027.9A CN104788792B (en) | 2015-05-11 | 2015-05-11 | A kind of method preparing the continuously extruded composite of high energy low temperature ball milling and the composite of the method preparation |
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| CN201510238027.9A CN104788792B (en) | 2015-05-11 | 2015-05-11 | A kind of method preparing the continuously extruded composite of high energy low temperature ball milling and the composite of the method preparation |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105585763A (en) * | 2016-03-24 | 2016-05-18 | 叶青 | UHMWPE plastic alloy |
| CN106046513A (en) * | 2016-08-16 | 2016-10-26 | 宜兴市灵谷塑料设备有限公司 | Method for manufacturing modified ultra-high-molecular-weight polyethylene for centrifugal pump |
| CN107602994A (en) * | 2017-09-06 | 2018-01-19 | 四川昌晟塬环保科技有限公司 | One kind enhancing unvulcanised thermal weld EPT rubber fire-resistant waterproof coiled material and preparation method thereof |
| CN114772591A (en) * | 2022-05-09 | 2022-07-22 | 厦门高容纳米新材料科技有限公司 | Method and equipment for low-temperature nano-conversion of soft material |
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| EP0748198B1 (en) * | 1994-03-01 | 2001-04-11 | The Procter & Gamble Company | Process for producing a surfactant treated, formed, polymeric web |
| CN1468897A (en) * | 2003-06-10 | 2004-01-21 | 上海英泰塑胶有限公司 | Composite polypropylene material containing potassium titanate whisker and glass fiber |
| CN102615802A (en) * | 2012-04-11 | 2012-08-01 | 大连交通大学 | Visual ultrahigh molecular weight continuous extrusion experimental device for polyethylene |
-
2015
- 2015-05-11 CN CN201510238027.9A patent/CN104788792B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0748198B1 (en) * | 1994-03-01 | 2001-04-11 | The Procter & Gamble Company | Process for producing a surfactant treated, formed, polymeric web |
| CN1468897A (en) * | 2003-06-10 | 2004-01-21 | 上海英泰塑胶有限公司 | Composite polypropylene material containing potassium titanate whisker and glass fiber |
| CN102615802A (en) * | 2012-04-11 | 2012-08-01 | 大连交通大学 | Visual ultrahigh molecular weight continuous extrusion experimental device for polyethylene |
Non-Patent Citations (1)
| Title |
|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105585763A (en) * | 2016-03-24 | 2016-05-18 | 叶青 | UHMWPE plastic alloy |
| CN106046513A (en) * | 2016-08-16 | 2016-10-26 | 宜兴市灵谷塑料设备有限公司 | Method for manufacturing modified ultra-high-molecular-weight polyethylene for centrifugal pump |
| CN107602994A (en) * | 2017-09-06 | 2018-01-19 | 四川昌晟塬环保科技有限公司 | One kind enhancing unvulcanised thermal weld EPT rubber fire-resistant waterproof coiled material and preparation method thereof |
| CN114772591A (en) * | 2022-05-09 | 2022-07-22 | 厦门高容纳米新材料科技有限公司 | Method and equipment for low-temperature nano-conversion of soft material |
| CN114772591B (en) * | 2022-05-09 | 2023-06-16 | 厦门高容纳米新材料科技有限公司 | Method and equipment for low-temperature nanocrystallization of soft material |
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