PHOTORESIST POLYMERS

QCM-D TO STUDY DISSOLUTION MECHANISMS IN PHOTORESIST POLYMERS

INTRODUCTION
Many newly developed photoresist
polymers swell when exposed to the
developing solution, which is used
when creating a microlithographic
structure with photoresist polymers.
For these polymers, the effects on the
rate of dissolution due to the swelling
process are poorly understood.
The study reported in this application
note explores the response of a thin
film to an aqueous alkaline solution
as a function of the composition of the
polymer as it changes. The study was
conducted in real time using Quartz
Crystal Microbalance with Dissipation
monitoring (QCM-D). The reported
data challenges the current models
of photoresist polymer film dissolution
mechanisms that do not take into
account the swelling properties of the
film.

Surface Plasmon Resonance (2 Channels/exchangeable cuvette)

Introduction:

Metal-organic frameworks (MOFs) are crystalline supramolecular assemblies that are built up from precisely defined subunits by coordination or covalent interactions [1]. MOFs are usually highly porous, and they offer a wide range of applications where incorporation of guest molecules are needed. Applications include fuel storage, catalysis, drug delivery and gas sensing. Recently a layer-by-layer (LbL) method for building such materials has been introduced, which offers more control on the MOF structure. [1,2]Surface Plasmon resonance (SPR) is a highly sensitive optical method that measures changes in refractive index (RI) near a metal surface, even as small changes as 10-6 RI units. [3] In the Kretschmann configuration, the SPR signal is excited and measured from the “dry side” of a metal coated sensor slide, which makes it possible to measure highly light-absorbing or turbid solutions. Due to the high sensitivity, SPR has traditionally been a tool for biochemists for measuring biomolecular interactions in solution. However, because the SPR phenomenon is not selective, it can also be used for nanoscale material science as well. Apart from only measuring relative changes in the intensity at fixed angles or angular position, the SPR Navi 200 also allows collection of the complete SPR curve with absolute angle information thus enabling optical constants and thickness determination of nanoscale films both in gas and liquid phases.

adsorption studies can provide valuable insight into the mechanism of asphaltene deposition.

ANALYSIS OF ASPHALTENES AND CRUDE

OIL ADSORPTION ON SURFACES USING QCMD

Surface interactions of asphaltenes

in crude oil represent

an important issue for

the petrochemical industry.

QCM-D technology is helpful

for evaluating different approaches

to solve these problems.

In particular, the ability

to monitor different structural

arrangements of adsorbed

materials is useful for understanding

how asphaltenes adsorb

to surfaces.

QS 405-25-1

Introduction

Every day, the complex petroleum

industry faces the challenge of

handling fouling, altered wettability

and coking. A major cause of these

problems is the adsorption of petroleum

heavy ends at solid/liquid

interfaces that occurs at different

stages of oil production. Among

heavy ends in petroleum, asphaltenes

are often considered the

most problematic because of their

chemical nature and their tendency

to aggregate and form deposits under

certain pressure, temperature

and composition conditions.

CONCLUSION

QCM-D enables real-time characterization of asphaltene (in crude oil,

or purified from crude oil) adsorption onto different surfaces. The adsorbed

amounts and characteristics of adsorption depend on the solubility

state of the asphaltene as well as its origin. Furthermore, surface

adsorption varies to a small extent between different hydrophilic sensor

coatings.

Tensiometer Kulim Kht Palm Oil Industry

Cloud point

Cloud Point is the temperature at which the oil begins to cloud resulting from crystallisation under controlled cooling. The CP is related to the unsaturation of the oil. In general the higher is the unsaturation, lower will be the CP. The initial quality of crude palm oil CPO (diglycerides, FFA,…) has strong influence of the CP of the oleins. Due to often misinterpretations here the AOCS Official Method Cc 6-25 . (1993)

Definition : The cloud point is that temperature at which, under the conditions of this test, a cloud is induced in the sample caused by the first stage of crystallization.

Scope : Applicable to all normal animal and vegetable fats.

Apparatus

1. Oil sample bottle–115 mL (4 oz).
2. Thermometer–range –2–68°C, AOCS Specification H 6-40.
3. Water bath-made up of water, chipped ice and water; or chipped ice, salt and water, depending on the temperature required. The temperature of the cloud point bath shall not less than 2˚C, nor more than 5˚C below the cloud point. Either a beaker or insulated container is convenient for the test.

Procedure

1. The sample must be completely dry before making the test. If the sample contains traces of moisture, it should be filtered through suitable filter paper. Heat 60-75 g of sample to 130˚C (see Notes, 1) just before making the test. Pour 45 mL of the heated fat into the oil sample bottle.
2. Begin to cool the bottle and contents in the water bath, stirring enough to keep the temperature uniform. When the sample has reached a temperature about 10˚C above the cloud point, begin stirring steadily and rapidly in a circular motion so as to prevent supercooling and solidification of fat crystals on the sides or bottom of the bottle.
3. From this point on, do not remove the thermometer from the sample : doing so may introduce air bubbles which will interfere with the test. The test bottle is maintained in such a position that the upper level of the sample in the bottle is level with the water in the bath.
4. Remove the bottle from the bath and inspect regularly. The cloud point is that temperature at which that portion of the thermometer immersed in the oil is no longer visible when viewed horizontally through the bottle and sample.
   
   
   Notes

1. It is essential that the sample be heated to 130˚C to destroy any crystal nuclei.

Krafft point

The temperature (more precisely, narrow temperature range) above which

the solubility of a surfactant rises sharply. At this temperature the solubility

of the surfactant becomes equal to the critical micelle concentration. It is

best determined by locating the abrupt change in slope of a graph of the

logarithm of the solubility against t or 1/T.

or in other word

The Krafft temperature (also known as Krafft point, or critical micelle temperature) is the minimum temperature at which surfactants form micelles. Below the Krafft temperature, there is no value for the critical micelle concentration (CMC), i.e., micelles cannot form. The Krafft temperature is a point of phase change below which the surfactant remains in crystalline form, even in aqueous solution.
Surfactants in such a crystalline state will only solubilize and form micelles if another surfactant assists it in overcoming the forces that keep it crystallized, or if the temperature increases, thus causing entropy to have a stronger force and encouraging the crystalline structure to break apart

Surface Tension measurement with Force Tensionmeter

Surface tension, γ

A molecule in the bulk of a liquid experiences

an equally attractive force in all

directions, but at the surface there is more

attractive force in the direction of the bulk

than away from it. This reduced attraction

at the liquid-gas boundary gives rise to the

measurable property of surface tension.

At the liquid-liquid phase boundary, it is

referred to as interfacial tension. Surface

tension can be measured with optical,

force, volumetric or bubble tensiometers,

while interfacial tension can be measured

with force and optical tensiometers.

Contact angle, θ

Surface tension alone does not explain

the shape of a drop along a solid. Interaction

between the liquid and solid can be

attractive or repulsive. When attracted

by the solid, the liquid spreads, forming

short drops with low contact angles. If

repelled, the drops are taller, rounder and

have high contact angles. The lotus effect

is a special case of water repelling, or

hydrophobic, behavior. The microstructuring

of a leaf makes the surface superhydrophic,

causing a rain droplet to roll

off by itself.

Surface free energy

Surface free energy is surface tension for

solids. Like in liquids, surface molecules in

solids have more attractive forces towards

the bulk than away from it. This leaves the

surface molecules inclined to attract neighbouring

substances, so the higher the

surface free energy the easier it is to wet a

substrate. In contrast to liquids, the surface

free energy of solids cannot be measured

with tensiometry but via contact angle

measurements with a range of liquids.

http://www.attension.com/force-tensiometers.aspx

Kulim Kht SPR technology

Hydrogen would be a great and clean fuel, but how do we store it ?

Hydrogen is the most common chemical element in the universe. And since it is involved in the transformation of energy on the sun, you don’t have to be a rocket scientist to realize it has a potential as a fuel. In the presence of oxygen, hydrogen is extremely flammable and it could therefore be used in combustion processes.

It is believed that hydrogen gas could be a strong candidate to replace fossil fuel in cars and as energy source also for very small devices, such as mobile telephones. Hydrogen is present in ordinary water, which we have lots of. When it combusts, it creates no carbon dioxide which would affect global warming.

However, there are some problems. Firstly, it takes a lot of energy to break out hydrogen from water. Secondly, hydrogen is evanescent and highly flammable, making it difficult to store and transport. Let’s hope that scientists figure these issues out so that we can start utilizing this easily accessible and environment friendly fuel !

We contribute by providing  SPR technologies. These technologies, utilized in combination, have been used by researchers who try to analyze how hydrogen can be deposited in a bead of nanoparticles. Within us there is eagerness to contribute more to the development of cleaner technologies.

Visit KHT at ICENV 2010 on the13th to the 15th of December

http://www.attension.com/icenv-2010-penang-malaysia.aspx

http://www.ksvnima.com/icenv-2010

NEW INNOVATIVE TECHNIQUE FOR ACCELERATED CORROSION MEASUREMENT & AUTOMATIC INHIBITOR CHEMICAL OPTOMIZATION

Traditional HPHT Autoclave designs have been enhanced by the introduction of real-time corrosion measurement instruments and probes, to accurately reproduce the multiphase flowing field conditions of operating pipelines and industrial environments.

Corrosion Measurement - Early Practices

Shear Stress Measurement- Effect of Velocity on Corrosion- Laminar Flow Studies

Corrosion Modeling- Multiphase Studies Accelerated Pipeline Integrity

Automated Inhibitor Injection (A.I.I.)- “Feedback” Chemical Pump Control

Corrosion Measurement

For many decades’ production and pipeline operators used simple corrosion coupons as an intermittent corrosion weight loss measurement. NACE, ASTM and others made exhaustive attempts to upgrade the method, Conducting Corrosion Coupon Tests in Plant Equipment, ASTM G4-84 originating (A224-39) in 1939.

Additional test methods were developed by NACE and others, as example TM01-77-96, Laboratory Testing of Metals for Resistance to Sulfide Stress Corrosion Cracking in H2S Environments. The standard addressed “the testing of metals for resistance to cracking failure under combined action of tensile stress and corrosion in aqueous environments containing Hydrogen Sulfide (H₂S)”.

Shear Stress Measurement

The 1995 NACE Publication 5A195 State Of-The-Art on Controlled Flow Laboratory Corrosion Tests was a “compilation of experimental techniques intended to provide the most up to date information available at the time on evaluating the effect of velocity on corrosion”, called Shear Stress. Included in NACE #5A195 (but not limited to) were the contents:

• Interpretation of Lab Measurements

• Philosophy Behind Experimental Design

• Experimental Systems

• References

• Appendix B Governing Equations:

• Rotating Disk

• Rotating Cylinder

• Impingement Jet

• Flow-Loop System

In 1996 NACE Publication #1D196 Laboratory Test Methods for Evaluating Oilfield Corrosion Inhibitors, coupled the above NACE #5A195 with the effects of chemical inhibitor applications under multiphase flow controlled test equipment for lab simulations.

During recent decades, ER/LPR became viable techniques adapted from lab studies and applied in the form of probes and instruments developed for long-term field studies.

Modern electronic components and high speed data acquisition evolution allowed a more rapid response corrosion rate measurement to be made in real time. The new probe/instrument system could be used to make measurements not only in electrolytic, but in non-conductive gas environments as well. The rapid response Systems have been readily accepted by the corrosion community as touted in NACE Papers 1997 #288 A Critical Comparison of Corrosion Monitoring Techniques in Industrial Applications, and later in NACE 2000 #00090 Field Trial Results of a New Rapid Corrosion Monitoring System

Automated Inhibitor Injection

Complimenting the high shear and impingement measurements, new Automated Inhibitor Injection (A.I.I.) systems are in operation since 1998 using the rapid response corrosion rate output signal to determine and control the optimum inhibitor chemical dose rate using variable flow rate inhibitor chemical injection pumps.

CONCLUSION

Cost of corrosion and its associated long terms costs can be significantly reduced with properly configured laboratory HPHT simulation systems, in combination with the newest state-of-the-art A.I.I. skid installations. The initial cost of these systems is quite small compared to the potential savings in material assets, non-productive downtime, the global environment and personnel safety.

G. W. Mazurk Sr. Vice President Cortest, Inc.

www. cortest.com

Autoclave HPHT Cotest Kulim Kht RESEARCH-GRADE DUAL AUTOCLAVE SYSTEM

RESEARCH-GRADE DUAL AUTOCLAVE SYSTEM

Research Project:

Physical and corrosion properties of pipeline, downhole and refinery steels and alloys

Optimization of anti-corrosion chemicals inhibitor formulations and dosage rates

Cost Savings Relation of Laboratory Test Results to Field Operations:

Materials of Construction

Material’s selection decision can be greatly improved by evaluating the material’s performance at high temperature and high pressure in a laboratory autoclave. These systems are very versatile, permitting short term tests for inhibitor screening, medium term electrochemical evaluations, and very long-term exposures. From these results, informed decisions can be made to optimize cost vs. performance of materials used in pipelines, valves, fittings, pumps, pressure vessels, and heat exchangers.

Corrosion Inhibitors

Inhibitor performance can be evaluated using multiple techniques in autoclave systems. Shear stress measurements using jet impingement or rotating cylinder tests can accurately define inhibitor performance, permitting selection of proper formulations.

PURPOSE OF RESEARCH

This dual autoclave system is necessary to accelerate tests screening results and support the I0 Dynamic Multiphase Test Loop according to ASTM G170-01a, Paragraph 4, Summary of Guide, attached.

In accordance with ASTM and NACE Test Method Standards; accurately simulate the physical field operating conditions and easily screen material samples fitting NACE and ISO recommended practices.

a) Study corrosion behavior and effects of field operations and oil/gas chemicals from down hole to refinery, including seawater, oxygen, CO₂/H₂S (and other gases) and effect of flow on the surfaces of subject screening material’s test specimen.

b) Characterize the corrosion product films that adhere on materials.

c) Study the effectiveness of the anti-corrosion inhibitor chemicals for all environments, from down hole to pipelines, to storage and refinery field applications.

d) Understand and apply the test results of the measured corrosion behavior and corrosion resistance.

LITERATURE REVIEW

Lab test equipments will fully conform to ASTM G170-01a Standard Guide for Evaluating & Qualifying Oilfield& Refinery Inhibitors in the Laboratory

www.cortest.com

Surface Plasmon Resonance (2 Channels/exchangeable cuvette)

Surface Plasmon Resonance has been established as a powerful method to monitor label-free biomolecular interactions in liquids. However, today SPR can deliver well beyond kinetics and equilibrium constants: you can expect more from SPR with SPR Navi 200.

SPR

SPR Navi 200, the versatile SPR system for surface science. Surface molecular interactions Nanoscale film properties, Langmuir-Blodgett films.

Self-assembled monolayers, Spin and dip-coated layers, Non-dielectric films

Application notes are provided at our web site: www.bionavis.com

SPR and Nanoscale films. Physics and material sciences Bio-material films SwellingAdsorption/absorption- Membrane properties, Gas sensors

Surface Plasmon Resonance has been established as a powerful method to monitor label-free biomolecular interactions in liquids. However, today SPR can deliver well beyond kinetics and equilibrium constants: you can expect more from SPR with SPR Navi 200.With SPR Navi 200 – an incident beam of p-polarized light strikes an electrically conducting gold layer at the interface of a glass sensor (high Refractive Index) and an external medium with low RI (gas or liquid).At a given angle, due to a resonance phenomenon, light is exciting surface plasmons at the interface – resulting in a reduced intensity of the reflected light.A slight change at the interface (e.g. a change in refractive index or nanoscale film thickness) will lead to a change in SPR signal – allowing precise measurements of nanoscale film properties as well as surface molecular interactions.

BioNavis’ SPR Navi 200 System uses an increased angular scan range that produces a complete SPR curve. This increased angular range allows you to simultaneously characterize surfaces in gas and/or liquid. This also allows you to check the quality of user-defined surfaces before sample injection. This broadens the scope of your measurements.In addition to traditional biophysical interaction phenomena, you can characterize optical constants and thicknesses of nanoscale structures.

You can measure:

Surface-molecular interactions, Nanoscale film properties :

Langmuir-Blodgett films Self-assembled monolayers

Spin-and dip-coated layers Non-dielectric films

Physics and material sciences- Bio-material films:

Swelling Adsorption/absorption Membrane properties

Gas sensors:

BioNavis Ltd was established to develop, manufacture, supply and support Surface Plasmon Resonance (SPR) based instruments and sensors for research and diagnos-tics. The Company was founded in 2006 by private inves-tors and professionals with several decades experience in scientific instrumentation, to take over and further advance the SPR technology primarily developed at VTT - Technical Research Centre of Finland. Counting the previous devel-opment at VTT, there are more than 15 years of accumu-lated development history in the BioNavis SPR technology. BioNavis holds several international patents related to the SPR techniques and its applications.The mission of BioNavis is to respond customer needs by developing sensors, methods and research instruments which have clearly better features and performance as compared to competitors, but with affordable price.

The SPR instruments are mainly targeted to research of molecu-lar interactions, and are used by researchers in physical chemistry, biochemistry, pharmaceutics, biotechnology, and medical diagnostics.SPR Navi 200 has been developed in collaboration with Dr. Janusz Sadowski who has been the main driver in the research of SPR technique at VTT for over 20 years, and Dr. Ulf Jönsson, the founder and former CEO of Biacore, the company that pioneered the use of SPR spectroscopy for protein interaction analysis.BioNavis Ltd is based in Tampere – Finland – and provides worldwide distribution and local customer support via its fully trained and capable global network of distribution partners.

Application notes are provided at our web site: www.bionavis.com

Biophysical Characterisation

Introduction to Biophysical Characterisation

using Dual Polarisation Interferometry

Dual Polarisation Interferometry (DPI) is a highly versatile, powerful analytical technique for

biophysical characterisation of proteins and other biomolecules. It extends the typical dynamic

measurements of conventional biosensors by including an additional quantitative, sub molecular,

conformational measurement.

DPI delivers a unique perspective on biochemistry, linking conformational changes to biochemical activity at a resolution normally associated with ‘big physics’.

DPI is an interferometric technique to derive dynamic information concerning the thickness,

density and mass of the molecular layer. As well as mass-based affinity and kinetic

determinations possible with other label-free optical and acoustic biosensor technologies, DPI

additionally provides real-time data on the orientation of the surface immobilised layer and

any conformational changes involved upon binding.

Two polarisations of light are passed through the sensor which consists of an upper ‘sensing’ layer and an embedded ‘reference’ layer. The output from each of the layers then combine producing two interference patterns which are detected by a camera. As molecules bind (or change shape) on the surface of the ‘sensing’ layer, they are probed by the evanescent field from the ‘sensing’ surface. This, in turn, changes both interference patterns. As material binds, the interference pattern shifts one way.

As material is removed from the surface, the interference pattern returns.

The AnaLight® Resolver software automatically analyses both sets of data and outputs the real time changes in the thickness, density and mass of the molecular layer. All of the calculations are based on classical optics theory and have been independently validated by, amongst others, the National Physics Laboratory (NPL) in the UK.

Potentiostat with autoclave

The potentiostatic test is usually performed to determine resistance to pit initiation at a given potential and to simulate galvanic situations using any of Gill AC 8 12 Field Machine and manual potentiostat set to a stable potential whilst recording the current. In the study of pitting the cyclic sweep method can have problems related to sweep rate and too much pitting propagation before sweep reversal. The use of individual samples held at potentials around the suspected pitting potential will allow the correct determination of the pitting potential.

CONTACT ANGLE MEASUREMENT

Contact Angle: Theory
The following is a short introduction to the concepts involved in the measurement of contact angles. Included is an introduction to the techniques involved and some practical advise. For those interested in further information a list of references appears at the end of this chapter.
What is contact angle?
Contact angle ,q, is a quantitative measure of the wetting of a solid by a liquid. It is defined geometrically as the angle formed by a liquid at the three phase boundary where a liquid, gas and solid intersect

It can be seen from this figure that low values of q indicate that the liquid spreads, or wets well , while high values indicate poor wetting. If the angle
q is less than 90 the liquid is said to wet the solid. If it is greater than 90 it
is said to be non-wetting. A zero contact angle represents complete wetting.

Hysteresis: For any given solid / liquid interaction there exists a range of contact angles which may be found. The measurement of a single static contact angle to characterize the interaction is no longer thought to be adequate. The value of static contact angles are found to depend on the
recent history of the interaction. When the drop has recently expanded the angle is said to represent the ‘advanced’ contact angle. When the drop has recently contracted the angle is said to represent the ‘receded’ contact angle. These angles fall within a range with advanced angles approaching a maximum value and receded angles approaching a minimum value.
The difference between the maximum(advanced) and minimum(receded) contact angle values is called the contact angle Hysteresis. A great deal of research has gone into analysis of the significance of hysteresis. It has been used to help characterize surface heterogeneity, roughness and mobility. You are recommended to the papers listed in the reference of this section for details on experiments regarding hysteresis.
Contact angle can also be considered in terms of the thermodynamics of the materials involved. This analysis involves the interfacial free energies between the three phases and is given by:
glv cos q = gsv - gsl
where glv ,gsv and gsl refer to the interfacial energies of the liquid/vapor, solid/vapor and solid/liquid interfaces.